Color light-sensitive material

ABSTRACT

A color light-sensitive material is provided, comprising on a support at least a light-sensitive silver halide, a binder, a dye providing substance which provides a mobile dye in inverse-relationship to the reduction reaction of silver ion to silver, and a development inhibitor precursor of the general formula (I): 
     
         PWR--Time--.sub.t AF                                       (I) 
    
     wherein PWR represents a group which releases (Time--hd tAF by being reduced; AF represents a group which serves as a development inhibitor after being released; Time represents a group which releases AF through a reaction following the release of --Time-- t  AF from PWR; and t represents an integer of 0 or 1. 
     In a preferred embodiment, the compound of the general formula (I) is represented by the general formula (II): ##STR1## In another embodiment, the compound of the general formula (II) is represented by the general formula (III): ##STR2##

This is a continuation of application Ser. No. 07/127,841, filed Dec. 2,1987, now abandoned.

FIELD OF THE INVENTION

The present invention relates to a color light-sensitive material. Moreparticularly, the present invention relates to a color light-sensitivematerial which can be effectively used to provide a positive dye imagein a diffusion transfer process.

BACKGROUND OF THE INVENTION

Various attempts have heretofore been made to prepare a colorlight-sensitive material capable of providing a positive dye image in adiffusion transfer process. U.S. Pat. Nos. 3,209,016, 3,362,819,3,597,200, 3,544,545, and 3,482,972, and Japanese Patent Application(OPI) No. 165054/84 describe processes which comprise formation of apositive dye image in a wet development process or heat developmentprocess using a color developing agent. Japanese Patent Application(OPI) Nos. 63618/76, 69033/78, 130927/79, 111628/74, 4819/77, and152440/84 (the term "OPI" as used herein means an "unexamined publishedapplication") describe processes which comprise formation of a positivedye image in a wet development process or heat development process usinga reductive nondiffusible, dye providing substance which releases amobile dye under an alkaline condition and/or under heating but whichdoes not release the dye upon reaction with exposed silver halide.Japanese Patent Application (OPI) Nos. 35533/78, 110827/78, 130927/79,164342/81, and 154445/84, European Patent 220746A, and U.S. Pat. Nos.4,356,249 and 4,358,525 disclose processes which comprise formation of apositive dye image in a wet development process or heat developmentprocess using a nondiffusible, dye providing substance which releases amobile dye upon reduction by a reductive substance (electron donorand/or electron transfer agent).

However, these known positive dye image formation processes have adisadvantage in recognition of image. That is, these processes canprovide only a positive dye image having a low density and a high stain.

SUMMARY OF THE INVENTION

It is therefore an object of the invention to provide a colorlight-sensitive material capable of providing a high image density andlow stain positive dye image which can be well recognized.

The above and other objects of the present invention will become moreapparent from the following detailed description and examples.

These objects of the present invention are accomplished with a colorlight-sensitive material, comprising on a support at least alight-sensitive silver halide, a binder, a dye providing substance whichprovides a mobile dye in inverse-relationship to the reduction reactionof silver ion to silver, and a development inhibitor precursor of thegeneral formula (I):

    PWR--Time--.sub.t AF                                       (I)

wherein PWR represents a group which releases (Time--_(t) AF upon beingreduced; AF represents a group which serves as a development inhibitorafter being released; Time represents a group which releases AF througha reaction following the release of --Time--_(t) AF from PWR; and trepresents an integer of 0 to 1.

DETAILED DESCRIPTION OF THE INVENTION

PWR will be first described in detail hereinafter.

PWR may correspond to a portion containing an electron accepting centerand an intramolecular nucleophilic displacement reaction center in acompound which undergoes an intramolecular nucleophilic displacementreaction after being reduced to release a photographic reagent asdisclosed in U.S. Pat. Nos. 4,139,389 and 4,139,379 and Japanese PatentApplication (OPI) No. 189333/84; a portion containing an electronaccepting quinonoid center and a carbon atom which binds the electronaccepting quinonoid center to a photographic reagent in a compound whichundergoes an intramolecular electron migration reaction after beingreduced to release the photographic reagent as disclosed in U.S. Pat.No. 4,232,107 and Japanese Patent Application (OPI) Nos. 101649/84 and88257/86; a portion containing an aryl group substituted by anelectrophilic group and an atom which binds the aryl group to aphotographic reagent (e.g., sulfur atom, carbon atom, or nitrogen atom)in a compound which undergoes cleavage of single bond after beingreduced to release the photographic reagent as disclosed in JapanesePatent Application (OPI) No. 142530/81 and U.S. Pat. Nos. 4,343,893 and4,619,884; a portion containing a nitro group and a carbon atom whichbinds the nitro group to a photographic reagent in a compound whichreleases the photographic reagent after accepting electrons as disclosedin U.S. Pat. No. 4,450,223; or a portion containing a dieminaldinitroportion and a carbon atom which binds the dieminaldinitro portion to aphotographic reagent in a dinitro compound which undergoes β-release ofthe photographic reagent after accepting electrons as disclosed in U.S.Pat. No. 4,609,610. However, compounds represented by the followinggeneral formula (II) are preferred. ##STR3##

In the general formula (II), ##STR4## corresponds to PWR. (Time--_(t) AFis bonded to at least one of R¹, R², and EAG.

The portion corresponding to PWR in the general formula (II) will befurther described hereinafter.

X represents an oxygen atom (--O--), a sulfur atom (--S--), or anitrogen atom-containing group ##STR5##

R¹, R² and R³ each represents a group other than a hydrogen atom, or amere bond.

R¹ and R³ each are preferably a substituted or unsubstituted alkylgroup, aryl group, heterocyclic residual group, acyl group, or sulfonylgroup.

R² is preferably a substituted or unsubstituted acyl group or sulfonylgroup. Any two of R¹, R², and R³ may be bonded to each other to form a5-membered to 8-membered ring.

The solid lines indicate a bond; and the broken lines indicate that atleast one thereof represents a bond.

EAG will be described later.

Among those compounds represented by the general formula (II), compoundsrepresented by the general formula (III) are preferred. ##STR6##

In the general formula (III), ##STR7## corresponds to PWR. Time--_(t) AFis bonded to at least one of R⁴ and EAG. The portion corresponding toPWR in the general formula (III) will be further described hereinafter.Y represents a divalent linking group which is preferably ##STR8## or--SO₂ --. X is as described above and preferably represents an oxygenatom.

R⁴ represents an atomic group which is bonded to X and Y to form a5-membered to 8-membered monocyclic or fused heterocyclic ringcontaining nitrogen atoms.

Preferred examples of portions corresponding to ##STR9## and sites atwhich --Time--_(t) AF may be bonded will be shown hereafter. ##STR10##

As EAG there may preferably be used a group represented by the generalformula (A) or (B): ##STR11##

In the general formula (A), Z₁ represents ##STR12## or --N<.

V_(n) ' represents an atomic group which forms a 3-membered to8-membered ring together with Z₁ and Z₂. The suffix n' represents aninteger of 3 to 8. In the case of V₃, V₄, V₅, V₆, V₇, and V₈, V_(n) 'represents --Z₃ --, --Z₃ --Z₄ --, --Z₃ --Z₄ --Z ₅ --, --Z₃ --Z₄ --Z₅--Z₆ --, --Z₃ --Z₄ --Z₅ --Z₆ --Z₇ --, and --Z₃ --Z₄ --Z₅ --Z₆ --Z₇ --Z₈--, respectively. Z₂ to Z₈ each represents ##STR13## --O--, --S--, or--SO₂ --, wherein Sub represents a mere bond (π bond), hydrogen atom, orsubstituent as described hereinafter. These groups represented by Submay be the same or different and may from 3-membered to 8-memberedsaturated or unsaturated carbon rings or heterocycles which may bebonded to each other. In the general formula (A), Sub is selected suchthat the sum total of the Hammet's substituent constant σp of thesubstituents is +0.09 or more, preferably +0.3 or more, particularly+0.45 or more.

In the general formula (B), n" represents an integer of 1 to 6. In thecase of U₁, U₂, U₃, U₄, U₅, and U₆, U_(n) " represents --Y₁, --Y₁ --Y₂,--Y₁ --Y₂ --Y₃, --Y₁ --Y₂ --Y₃ --Y₄, --Y₁ --Y₂ --Y₃ --Y₄ --Y₅, and --Y₁--Y₂ --Y₃ --Y₄ --Y₅ --Y₆, respectively. Y₁ to Y₆ each represents##STR14## wherein Sub' represents a mere bond (δ bond or π bond),hydrogen atom, or substituent as described hereinafter In the generalformula (B), Sub' is selected such that the sum total of the Hammett'ssubstituent constant σp of the substituents is +0.09 or more, preferably+0.3 or more, particularly +0.45 or more.

Examples of the substituents represented by Sub include substituted orunsubstituted alkyl groups, such as a methyl group, an ethyl group, asec-butyl group, a t-octyl group, a benzyl group, a cyclohexyl group, achloromethyl group, a dimethylaminomethyl group, a n-hexadecyl group, atrifluoromethyl group, a 3,3,3-trichloropropyl group, and amethoxycarbonylmethyl group; substituted or unsubstituted alkenylgroups, such as a vinyl group, a 2-chlorovinyl group, and a1-methylvinyl group; substituted or unsubstituted alkynyl groups, suchas an ethynyl group and a 1-propynyl group; a cyano group; a nitrogroup; halogen atoms, such as fluorine, chlorine, bromine, and iodine;substituted or unsubstituted heterocyclic residual groups, such as a2-pyridyl group, a 1-imidazolyl group, a benzothiazole-2-yl group, amorpholino group, and a benzoxazole 2 yl group; a sulfo group; acarboxyl group; substituted or unsubstituted aryloxycarbonyl oralkoxycarbonyl groups, such as a methoxycarbonyl group, anethoxycarbonyl group, a tetradecyloxycarbonyl group, a2-methoxylethycarbonyl group, a phenoxycarbonyl group, a4-cyanophenylcarbonyl group, and a 2-chlorophenoxycarbonyl group;substituted or unsubstituted carbamoyl groups, such as a carbamoylgroup, a methylcarbamoyl group, a diethylcarbamoyl group, amethylhexadecylcarbamoyl group, a methyloctadecylcarbamoyl group, aphenylcarbamoyl group, a 2,4,6-trichlorocarbamoyl group, anN-ethyl-N-phenylcarbamoyl group, and a3-hexadecylsulfamoylphenylcarbamoyl group; a hydroxyl group; substitutedor unsubstituted azo groups, such as a phenylazo group, a pmethoxyphenylazo group, and a 2-cyano-4-methanesulfonylphenylazo group;substituted or unsubstituted aryloxy or alkoxy groups, such as a methoxygroup, an ethoxy group, a dodecyloxy group, a benzyloxy group, a phenoxygroup, a 4-methoxyphenoxy group, a 3-acetylaminophenoxy group, a3-methoxycarbonylpropyloxy group, and a 2-trimethylammonioethoxy group;a sulfino group; a sulfeno group; a mercapto group; substituted orunsubstituted acyl groups, such as an acetyl group, a trifluoroacetylgroup,.an n-butyloyl group, a t-butyloyl group, a benzoyl group, a2-carboxybenzoyl group, a 3-nitrobenzoyl group, and a formyl group;substituted or unsubstituted aryl or alkylthio groups, such as amethylthio group, an ethylthio group, a t-octylthio group, ahexadecylthio group, a phenylthio group, a 2,4,5-trichlorothio group, a2-methoxy-5-t octylphenylthio group, and a 2-acetylaminophenylthiogroup; substituted or unsubstituted aryl groups such as a phenyl group,a naphthyl group, a 3-sulfophenyl group, a 4-methoxyphenyl group and a3-laurylaminophenyl group; substituted or unsubstituted sulfonyl groupssuch as a methylsulfonyl group, a chloromethylsulfonyl group, ann-octylsulfonyl group, an n-hexadecylsulfonyl group, a sec-octylsulfonylgroup, a p-toluenesulfonyl group, a 4-chlorophenylsulfonyl group, a4-dodecylphenylsufonyl group, a 4-dodecyloxyphenylsulfonyl group, and a4-nitrophenylsufonyl group; substituted or unsubstituted sulfinylgroups, such as a methylsulfinyl group, a dodecylsulfinyl group, aphenylsulfinyl group, and a 4-nitrophenylsulfinyl group substituted orunsubstituted amino groups, such as a methylamino group, a diethylaminogroup, a methyloctadecylamino group, a phenylamino group, anethylphenylamino group, a 3-tetradecylsulfamoylphenylamino group, anacetylamino group, a trifluoroacetylamino group, anN-hexadecylacetylamino group, an N-methylbenzoylamino group, amethoxycarbonylamino group, a phenoxycarbonylmethyl group, anN-methoxyacetylamino group, an amidiamino group, aphenylaminocarbonylamino group, a 4-cyanophenylaminocarbonylamino group,an N-ethylethoxycarbonylamino group, an N-methyldodecylsulfonylaminogroup, an N-(2-cyanoethyl)-p-toluenesulfonylamino group, and ahexadecylsulfonylamino group; substituted or unsubstituted sulfamoylgroups, such as a dimethylsulfamoyl group, a hexadecylsulfamoyl group, asulfamoyl group, a methyloctadecylsulfamoyl group, amethylhexadecylsulfamoyl group, a 2-cyanoethylhexadecylsulfamoyl group,a phenylsulfamoyl group, an N-(3,4-dimethylphenyl)-N-octylsulfamoylgroup, a dibutylsulfamoyl group, a dioctadecylsulfamoyl group, and abis(2-methoxycarbonyl)sulfamoyl group; substituted or unsubstitutedacyloxy groups, such as an acetoxy group, a benzoyloxy group, adecyloyloxy group, and a chloroacetoxy group; and substituted orunsubstituted sulfonyloxy groups such as a methylsulfonyloxy group, ap-toluenesulfonyloxy group, and a p-chlorophenylsulfonyloxy group. Thesegroups may preferably contain 0 to 40 carbon atoms.

Specific examples of EAG include aryl groups substituted by at least oneelectrophilic group, such as a 4-nitrophenyl group, a2-nitro-4-N-methyl-N-octadecylsulfamoylphenyl group, a2-N,N-dimethylsulfamoyl-4-nitrophenyl group, a2-cyano-4-octadecylsulfonylphenyl group, a 2,4-dinitrophenyl group, a2,4,6-tricyanophenyl group, a2-nitro-4-N-methyl-N-octadecylcarbamoylphenyl group, a2-nitro-5-octylthiophenyl group, a 2,4-dimethanesulfonylphenyl group, a3,5-dinitrophenyl group, a 2-chloro-4-nitro 5-methylphenyl group, a2-nitro-3,5-dimethyl-4-tetradecylsulfonylphenyl group, a2,4-dinitronaphthyl group, a 2-ethylcarbamoyl-4-nitrophenyl group, a2,4-bisdodecylsulfonyl5-trifluoromethylphenyl group, a2,3,4,5,6-pentafluorophenyl group, a 2-acetyl-4-nitrophenyl group, a2,4-diacetylphenyl group, and a 2-nitro-4-trifluoromethylphenyl group;substituted or unsubstituted heterocyclic rings, such as a 2-pyridylgroup, a 2-pyradyl group, a 5-nitro-2-pyridyl group, a5-N-hexadecylcarbamoyl-2-pyridyl group, a 4-pyridyl group, a3,5-dicyano-2-pyridyl group, a 5-dodecylsulfonyl-2-pyridyl group, a5-cyano-2-pyradyl group, a 4-nitrothiophene-2-yl group, a5-nitro1,2-dimethylimidazole-4-yl group, a 3,5-diacetyl-2-pyridyl group,and a 1-dodecyl-5-carbamoylpyridinium-2-yl group; and substituted orunsubstituted quinones such as a 1,4-benzoquinone-2-yl group, a3,5,6-trimethyl-1,4-benzoquinone-2-yl group, a3-methyl-1,4-naphthoquinone-2-yl group, a3,6-dimethyl-5-hexadecylthio-1,4-benzoquinone- 2-yl group, and a5-pentadecyl-1,2-benzoquinone-4-yl group. Besides the above describedvinylogs there can be used nitroalkanes and α-diketo compounds.

--Time--_(t) AF will be further described hereinafter.

Time represents a group which releases AF through a reaction triggeredby cleavage of a nitrogen-oxygen single bond. The suffix t represents 0or 1.

As groups represented by Time there have been known various groups asdescribed in Japanese Patent Application (OPI) Nos. 147244/86 and236549/86.

As development inhibitors represented by AF there may be used compoundscontaining mercapto groups bonded to heterocycles. Examples of suchcompounds include substituted or unsubstituted mercaptoazoles, such as1-phenyl-5-mercaptotetrazole, 1-(4 carboxyphenyl)-5-mercaptotetrazole,1-(3-hydroxyphenyl)-5-mercaptotetrazole,1-(4-sulfophenyl)-5-mercaptotetrazole,1-(3-sulfophenyl)-5-mercaptotetrazole,1-(4-sulfamoylphenyl)-5-mercaptotetrazole,1-(3-hexanoylaminophenyl)-5-mercaptotetrazole,1-ethyl-5-mercaptotetrazole, 1-(2-carboxyethyl) -5-mercaptotetrazole,2-methylthio 5-mercapto 1,3,4-thiadiazole,2-(2-carboxylethylthio)-5-mercapto 1,3,4-thiadiazole,3-methyl-4-phenyl-5-mercapto-1,2,4-triazole,2-(2-dimethylaminoethylthio)-5-mercapto-1,3,4-thiadiazole,1-(4-n-hexylcarbamoylphenyl)-2-mercaptoimdazole,3-acetylamino-4-methyl-5-mercapto-1,2,4-triazole, 2-mercaptobenzoxazole,2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercapto6-nitro-1,3-benzoxazole, 1-(1-naphthyl)-5-mercaptotetrazole,2-phenyl-5-mercapto-1,3,4-oxadiazole,1-[3-(3-methylureido)phenyl]-5-mercaptotetrazole,1-(4-nitrophenyl)-5-mercaptotetrazole, and5-(2-ethylhexanoylamino)-2-mercaptobenzimidazole; substituted orunsubstituted mercaptoazaindenes, such as 6-methyl-4-mercapto-1,3,3a,7-tetrazaindene,6-methyl-2-benzyl-4-mercapto-1,3,3a,7-tetrazaindene,6-phenyl-4-mercaptotetrazaindene, and4,6-dimethyl-2-mercapto-1,3,3a,7-tetrazaindene; and substituted orunsubstituted mercaptopyrimidines, such as 2-mercaptopyrimidine,2-mercapto 4-methyl-6-hydroxypyrimidine, and 2mercapto-4-propylpyrimidine. As other development inhibitors representedby AF there may be used heterocyclic compounds capable of producingimino silver. Examples of such compounds include substituted orunsubstituted benzotriazoles, such as benzotriazole,5-nitrobenzotriazole, 5-methylbenzotriazole, 5,6-dichlorobenzotriazole,5-bromobenzotriazole, 5-methoxybenzotriazole,5-acetylaminobenzotriazole, 5-n-butylbenzotriazole, 5-nitro6-chlorobenzotriazole, 5,6-dimethylbenzotriazole, and4,5,6,7-tetrachlorobenzotriazole; substituted or unsubstitutedindazoles, such as indazole, 5-nitroindazole, 3-nitroindazole,3-chloro-5-nitroindazole, 3-cyano indazole, 3-n-butylcarbamoylindazole,and 5-nitro-3-methanesulfonylindazole; and substituted or unsubstitutedbenzimidazoles, such as 5-nitrobenzimidazole, 4-nitrobenzimidazole,5,6-dichlorobenzimidazole, 5-cyano 6-chlorobenzimidazole, and5-trifluoromethyl-6-chlorobenzimidazole. Such a development inhibitormay be one which is released from an oxidation-reduction nucleus in thegeneral formula (I) by a reaction following an oxidation-reductionreaction in the development step, and then becomes a developmentinhibiting compound which will then be converted to a compound havingsubstantially no development inhibiting effect or remarkably smalldevelopment inhibiting effect.

Specific examples of such a development inhibitor include1-(3-phenoxycarbonylphenyl)-5-mercaptotetrazole,1-(4-phenoxycarbonylphenyl)-5-mercaptotetrazole,1-(3-maleimidophenyl)-5-mercaptotetrazole,5-(phenoxycarbonyl)benzotriazole,5-(p-cyanophenoxycarbonyl)benzotriazole,2-phenoxycarbonylmethylthio-5-mercapto-1,3,4-thiadiazole,5-nitro-3-phenoxycarbonylindazole,5-phenoxycarbonyl-2-mercaptobenzimidazole,5-(2,3-dichloropropyloxycarbonyl)benzotriazole,5-benzyloxycarbonylbenzotriazole,5-(butylcarbamoylmethoxycarbonyl)benzotriazole,5-(butoxycarbonylmethoxycarbonyl)benzotriazole,1-(4-benzoyloxyphenyl)-5-mercaptotetrazole,5-(2-methanesulfonylethoxycarbonyl)-2-mercaptobenzothiazole,1-[4-(2-chloroethoxycarbonyl)phenyl]-2-mercaptoimidazole,2-[3-{thiophene-2-yl-carbonyl}propyl]thio-5-mercapto-1,3,4-thiadiazole,5-cinnamoylaminobenzotriazole,1-(3-vinylcarbonylphenyl)-5-mercaptotetrazole,5-succinimidomethylbenzotriazole,2-[4-succinimidophenyl]-5-mercapto-1,3,4-oxadiazole, 3-[4-benzo-1,2-isothiazole-3-oxo-1,1-dioxy-2-yl)phenyl]-5-mercapto-4-methyl-1,2,4-triazole,and 6-phenoxycarbonyl 2-mercaptobenzoxazole.

These development inhibitors may be bonded to Time, R¹, R², R³, R⁴, orEAG via a portion of development inhibitor which serves to inhibit uponrelease (e.g. S atom in --SH, and N atom in an amino group).

Specific examples of the development inhibitors according to the presentinvention represented by the general formula (I) are shown below.##STR15##

Examples of the process for the synthesis of the compounds employed inthe present invention are described in European Patent 220746A andJapanese Patent Application (OPI) No. 244048/87, which are incorporatedherein by reference.

In order to facilitate the understanding of the present invention,specific examples of the process for the synthesis of the presentcompound will be described hereinafter. Unless otherwise specified, allparts, percentages and proportions are by weight.

(I) Synthesis of Compound AF-3 Synthesis Example I-1 Synthesis ofN-methyl-N-octadecyl-3-nitro-4-chlorobenzamide

105.7 g of 3-nitro-4-chlorobenzoic acid and 800 ml. of acetonitrile weremixed. 68.6 g of thionyl chloride was added to the admixture. Theadmixture was heated under reflux for 4 hours. After being cooled, thesolvent was removed from the solution. The residual material wasdissolved in chloroform. 63.5 g of triethylamine was then added to thesolution. The admixture was cooled to a temperature of 5° C. Achloroform solution of 148.6 g of N-methyloctadecylamine was addeddropwise to the admixture. After the reaction was completed, water wasadded to the solution. The admixture was subjected to separation. Theorganic phase was dried over anhydrous sodium sulfate. The inorganicmaterial was filtered out, and the solvent was removed therefrom. Theresidual material was then recrystallized from a 1:3 mixture ofacetonitrile and methanol. (Yield: 186 g (76.0%); m.p.: 55°-56° C.)

Synthesis Example I-2 Synthesis of 5-t-butyl-3-hydroxyisoxazole

583.7 g of hydroxylamine hydrochloride was dissolved in 2 l of a 4Naqueous solution of sodium hydroxide. 2 l of ethanol was added to thesolution under cooling with ice. A 1:1 mixture of a 4N aqueous solutionof sodium hydroxide and ethanol was added to the solution so that the pHthereof was adjusted to 10.0. 1,380 g of ethyl pivaloylacetate and a 1:1mixture of a 4N aqueous solution of sodium hydroxide and ethanol weresimultaneously added dropwise to the solution in such a manner that thepH of the reaction solution was 10±0.2 and the temperature thereof was0° to 5° C. After the dropwise addition was finished, the reactionmixture was stirred at room temperature for 2 hours, and then pouredinto 6 kg of concentrated hydrochloric acid. The reaction mixture wasallowed to stand for 12 hours. The resulting crystal was filtered off,thoroughly washed with water, and then dried. (Yield: 770 g (68.2%);m.p.: 99°-101° C.)

Synthesis Example I-3 Synthesis of5-t-butyl-2-(4-N-methyl-N-octadecylcarbamoyl-2-nitrophenyl)-3-isoxazolone

300 ml of dimethylformamide was added to 34.1 g ofN-methyl-N-octadecyl-3-nitro-4-chlorobenzamide, 12.4 g of5-t-butyl-3-hydroxyisoxazole, and 12.4 g of potassium carbonate. Theadmixture was then allowed to react at a temperature of 100° C. for 5hours. The solvent was removed under reduced pressure. Ethyl acetate andwater were added to the reaction mixture. The admixture was stirred. Theorganic phase was taken and subjected to silica gel columnchromatography to fractionate the main product therefrom. The mainproduct was then recrystallized from an n-hexane-ethyl acetate mixture.(Yield: 18.0 g (43.1%); m.p.: 64° C.)

Synthesis Example I-4 Synthesis of4-chloromethyl-5-t-butyl-2-(4-N-methyl-N-octadecylcarbamoyl-2-nirophenyl)-3-isoxazolone

36 g of5-t-butyl-2-(4-N-methyl-N-octadecylcarbamoyl-2-nitrophenyl)-3-isoxazolone,5.7 g of paraformaldehyde, and 10.3 g of zinc chloride were mixed with250 ml of acetic acid. The reaction mixture was then allowed to react ata temperature of 100° C. for 20 hours with hydrogen chloride gas bubbledthereinto. After the reaction was completed, the reaction mixture wascooled and then put in an ice water bath. The resulting solidprecipitate was filtered off, dissolved in chloroform, and then purifiedby column chromatography. (Yield: 10.0 g (25.6%); m.p.: 77° C.)

Synthesis Example I-5 Synthesis of Compound AF-3

40 g of5-t-butyl-2-(4-N-methyl-N-octadecylcarbamoyl-2-nitrophenyl)-3-isoxazoloneobtained in Synthesis Example I-4 and 12 g of1-phenyl-5-mercaptotetrazole were dissolved in acetone. 14 g ofpotassium carbonate was added to the admixture. The admixture was thenstirred at room temperature for 3 hours. The resulting inorganicmaterial was filtered out, and the residue was then recrystallized frommethanol to obtain 33 g (67% yield) of colorless crystals. (m.p. 66°-68°C.)

(II) Synthesis of Compound AF-9 Synthesis Example II-1 Synthesis of4-chloro-3-nitro-N-methyl-N-hexadecylbenzenesulfonamide SynthesisExample II-1-1 Synthesis of 4-chloro-3-nitrobenzenesulfonyl chloride

1,250 ml of phosphorus oxychloride was added dropwise to a mixture of1,280 g of potassium 4-chloro-3-nitrobenzenesulfonate, 1,150 ml ofacetonitrile, 250 ml of sulfolane, and 30 ml of dimethylacetamide insuch a manner that the internal temperature thereof was kept at 60° to70° C. After being allowed to react at a temperature of 73° C. for 3hours, the reaction mixture was cooled with water, and 400 ml of waterwas gradually added to the reaction mixture. The cooled reaction mixturewas then added to 5 l of ice water. The resulting crystals were filteredoff, washed with water, and then dried. (Yield: 1,060 g (84%); m.p.:55°-56° C.)

Synthesis Example II-1-2 Synthesis of 4-chloro3-nitro-N-hexadecylbenzenesulfonamide

1 l of dichloromethane was added to 800 g of4-chloro-3-nitrobenzenesulfonyl chloride. The admixture was cooled to atemperature of 0° C. A mixture of 600 g of hexadecylamine, 251 ml oftriethylamine, and 780 ml of dichloromethane was added dropwise to thesolution in such a manner that the temperature thereof was kept at 20°to 30° C. After being allowed to react at room temperature for 20 hours,dichloromethane was removed from the reaction mixture under reducedpressure. The residue was dissolved in 3 l of methanol under heating.The solution was gradually cooled to room temperature wherecrystallization took place. 3 of methanol was then added to thesolution. The solution was cooled with ice to induce crystallization.The crystals were then

filtered off and dried. (Yield: 1,020 g (88%); m.p.: 91°-93° C.)

Synthesis Example II-1-3 Synthesis of4-chloro-3-nitro-N-methyl-N-hexadecylbenzenesulfonamide

170 g of 4-chloro-3-nitro-N-hexadecylbenzenesulfonamide was dissolved in640 ml of acetone. 79 g of potassium carbonate, 400 ml of polyethyleneglycol, and 71 g of dimethylsulfuric acid were added to the solution.The admixture was heated under reflux for 5 hours. 240 ml of acetone wasadded to the solution. 870 ml of water was then added dropwise to thesolution in such a manner that the temperature thereof was kept at 40°C. Upon cooling to room temperature, crystallization occurred. Thecrystals were filtered off, washed with water and methanol, and dried.(Yield: 169 g (97%); m.p.: 74°-75° C.)

Synthesis Example II-2 Synthesis of Compound AF-9 Synthesis ExampleII-2-1 Synthesis of 5-t-butyl-2-(4-N-methyl-N-hexadecylsulfamoyl2-nitrophenyl)-3-isoxazolone

470 g of 4-chloro-3-nitro-N-hexadecylbenzenesulfonamide obtained inSynthesis Example II-1-3, 169 g of 5-t-butyl-3-hydroxyisoxazole obtainedin Synthesis Example I-2, 168 g of potassium carbonate, and 1.2 l ofdimethyl sulfoxide were mixed. The reaction mixture was then allowed toreact at a temperature of 65° C. for 6 hours. The reaction mixture wasthen poured into ice water. The resulting crystals were filtered off,washed with water, and dried. (Yield: 576 g (100%); m.p.: 67°-68° C.)

Synthesis Example II-2-2 Synthesis of5-t-butyl-4-chloromethyl-2-(4-N-methyl-N-hexadecylsulfamoyl-2-nitrophenyl)-3-isoxazolone

550 g of 5-t-butyl-2-(4-N-methyl-N-hexadecylsulfamoyl-2-nitrophenyl)3-isoxazolone, 200 g of zinc chloride, 200 g of paraformaldehyde, and1.5 l of acetic acid were mixed. The reaction mixture was then heatedunder reflux for 10 hours with hydrogen chloride gas bubbled thereinto.

After being cooled, the reaction mixture was poured into water. Theresulting crystals were filtered off and then recrystallized from a 1:4mixture of aceto nitrile and methanol. (Yield: 585 g (96%); m.p.: 56°C.)

Synthesis Example II-2-3 Synthesis of Compound AF-9

250 g of5-t-butyl-4-chloromethyl-2-(4-N-methyl-N-hexadecylsulfamoyl-2-nitrophenyl)-3-isoxazoloneand 75 g of 1-phenyl-5-mercaptotetrazole were dissolved in 500 ml ofacetone. 60 g of potassium carbonate and 5 g of potassium iodide wereadded to the solution, followed by stirring at room temperature for 2hours. The reaction mixture was poured into a dilute hydrochloric acidaqueous solution and then extracted with ethyl acetate. The extract waswashed with water and concentrated under reduced pressure. One liter ofethanol and 100 ml of ethyl acetate were added to the residue to effectrecrystallization. (Yield: 250 g (82%); m.p.: 73°-75° C.)

(III) Synthesis of Compound AF-10 Synthesis Example III-1 Synthesis of5-phenyl-3-hydroxyisoxazole

40 g of sodium hydroxide was dissolved in 200 ml of water and 300 ml ofethanol. 69.5 g of hydroxylamine hydrochloride was added to thesolution. A mixed solution of 2N sodium hydroxide and a 3:2 mixture ofethanol and water was added to the solution so that the pH thereof wasadjusted to 10.0. 192 g of ethyl benzoylacetate and a mixed solution of2N sodium hydroxide and a 3:2 mixture of ethanol and water were addeddropwise to the solution at the same time under cooling with ice in sucha manner that the pH thereof was 10±0.3. After the dropwise addition wasfinished, the solution was stirred at room temperature for 3 hours. Thereaction mixture was then poured into a mixture of 500 g of conc.hydrochloric acid and 500 g of ice. 2.5 l of ethanol was added to thereaction mixture. The reaction mixture was heated under reflux for 3hours. 2 l of water was added to cool the solution. The resultingcrystals were filtered off, washed with water, and dried. (Yield: 98 g(61%); m.p.: 150°-151° C.)

Synthesis Example III-2 Synthesis of4-chloro-3-nitro-N-methyl-N-octadecylbenzenesulfonamide

300 ml of chloroform was added to 100 g of4-chloro-3-nitrobenzenesulfonyl chloride. The solution was then cooledto a temperature of 0° C. A chloroform solution of 84.3 g ofmethyloctadecylamine was added dropwise to the solution. 39.5 g oftriethylamine was then added dropwise to the solution while thetemperature thereof was kept at 0° to 10° C. The solution was stirred atroom temperature for 1 hour. Chloroform was removed from the solutionunder reduced pressure. 500 ml of methanol was added to the residue. Thereaction mixture was heated to complete dissolution. The solution wascooled., The resulting crystals were filtered off and dried. (Yield: 109g (71%); m.p.: 86°-87° C.)

Synthesis Example III-3 Synthesis of Compound AF-10

Compound AF-10 was prepared in accordance with the process stepsdescribed above for Synthesis Examples II-2-1 to II-2-3 for CompoundAF-9. (m.p.: 117°-118° C.)

The present compounds may be incorporated in a silver halidephotographic material in accordance with the process describedhereinafter. These compounds may be reduced in electron migration pathsrepresented by the arrow in the following equation to release adevelopment inhibitor. ##STR16##

If a negative silver emulsion which is commonly used is used, thisreductive substance (RE) is used and consumed for the reduction ofsilver halide depending on the degree of exposure. Therefore, thisreductive substance is used in the reaction with the present compound ofthe general formula (I) in an amount inverse-relationship to the degreeof exposure, i.e. the amount left unused for the reduction of silverhalide. This means that the development inhibitor is released more atportions less exposed to light. On the contrary, if an auto positiveemulsion is used, silver halide is reduced at unexposed portions unlikein the case of negative emulsion. Therefore, this means that thereaction of the present compound of the general formula (I) with thereductive substance occurs more and the development inhibitor isreleased more at portions more exposed to light.

As described above, the compound employed in the present invention isreleased less at portions to be developed (portions where the reactionof silver halide with the reductive substance occurs) and more atnon-developed portions. For the purpose of adjusting (normallyimproving) the ratio of the amount of the development inhibitor releasedat portions to be developed to that at non-developed portions or likepurposes, a reductive substance called electron transfer agent (ETA)represented by the following equation may be used in combination withthe above described reductive substance. ##STR17##

In the present invention, the combined use of a dye providing substance(positive dye providing substance) which provides a mobile dye ininverse-relationship to the reduction reaction of silver ion to silverwith a development inhibitor precursor of the general formula (I) canimprove the image density without generation of stain. The reason forthis effect is believed to be as follows. That is, the compound of thegeneral formula (I) releases a development inhibitor at non developedportions to inhibit fog development of silver halide. This can inhibitthe positive dye providing substance from undergoing anoxidation-reduction reaction with silver halide at non-developedportions of silver halide or the reductive substance from undergoingundesired reaction with silver halide. As a result, a mobile dye isproduced more at non developed portions. The development inhibitor isreleased less at the developed portions. Therefore, the reaction ofsilver halide with a positive dye providing substance or the reaction ofsilver halide with a reductive substance occurs thoroughly, eliminatingthe possibility of stain generation.

The amount of the development inhibitor precursor of the general formula(I) to be used depends on the type of AF but is normally in the range of1×10⁻⁷ to 1 mol, preferably 1×10⁻³ to 1×10⁻¹ mol, per mol of silverhalide, or in the range of 1×10⁻³ to 1×10² mol, preferably 1×10⁻² to 10mol, per mol of positive dye providing substance as describedhereinafter. These development inhibitor precursors may be used singlyor in combination. These development inhibitor precursors may be used incombination with any suitable known development inhibitors.

As a suitable dye providing substance there may be used a compound ofthe general formula (CI):

    (Dye--X).sub.n --Y                                         (CI)

wherein Dye represents a dye group, a dye group which has beentemporarily shifted to shorter wavelengths, or a dye precursor group; Xrepresents a simple bond or a connecting group; Y represents a groupwhich controls the diffusibility of a compound represented by(Dye--X)_(n) --Y or releases Dye and then differentiates between the Dyethus released and (Dye--X)_(n) --Y in the diffusibility ininverse-relationship to light-sensitive silver salts having a latentimage distributed imagewise; and n represents an integer of 1 or 2, withthe proviso that when n is 2, the two (Dye--Y)'s may be the same ordifferent.

Typical examples of a dye providing substance (positive dye providingsubstance) which provides a mobile dye in inverse-relationship to thereduction of silver ion to silver include:

i. A dye providing substance (i.e., a dye developing agent which becomesmobile under an alkaline condition and/or under heating and becomesimmobile when oxidized by development.

ii. A reductive nondiffusible dye providing substance which releases amobile dye under an alkaline condition and/or under heating but doesn'trelease a dye when oxidized by development.

iii. A nondiffusible dye providing substance which undergoes a reactionwith a reductive substance left unconsumed in the development to releasea mobile dye.

Preferred among those belonging to substances ii and iii are substanceswhich have been made immobile by known ballast groups.

As positive dye providing substances belonging to substance i there maybe used dye developing agents as described in U.S. Pat. Nos. 3,134,764,3,362,819, 3,597,200, 3,544,545, and 3,482,972, and Japanese PatentApplication (OPI) No. 165054/84, incorporated herein by reference.

As positive dye providing substances belonging to substance ii there maybe used compounds as described in Japanese Patent Application (OPI) Nos.63618/76, 69033/78, 130927/79, 111628/74, and 4819/77, incorporatedherein by reference.

In the present invention there may be particularly preferably usedpositive dye providing substances belong to substance iii. Examples ofpositive dye providing substances belonging to substance iii will bedescribed hereinafter.

An example of such positive dye providing substances is a BEND compoundas disclosed in Japanese Patent Application (OPI) No. 110827/78. In asimplified equation, such a BEND compound undergoes an intramolecularnucleophilic displacement reaction containing the undermentionedreduction to release a mobile dye. ##STR18## wherein R²¹ to R²⁴ eachrepresents a substituent such as alkyl group.

Another example of such positive dye providing substance is a compoundas disclosed in Japanese Patent Application (OPI) No. 110828/78. In theundermentioned simplified equation, a nitro group which is anucleophilic precursor undergoes an intramolecular nucleophilicdisplacement reaction by reduction to release a mobile dye. ##STR19##wherein R²¹ and R²² each represents a substituent such as alkyl group;and R²³ represents a hydrogen atom or a substituent such as alkyl group.

A further example of such positive dye providing substances is acompound as disclosed in Japanese Patent Application (OPI) No.130927/81. In the undermentioned simplified equation, such a compoundundergoes the following reaction to release a mobile dye. ##STR20##wherein R represents a substituent such as alkyl group; and Ballrepresents a ballast group.

A further example of such positive dye providing substances is acompound as disclosed in U.S. Pat. No. 4,444,867 and Japanese PatentApplication (OPI) No. 196266/83. In a simplified equation, such acompound undergoes the following reaction to release a mobile dye.##STR21##

A further example of such positive dye providing substances is acompound as disclosed in Japanese Patent Application No. 88625/86. Sucha compound is represented by the undermentioned general formula (CII).In the general formula (CII), the N--X bond is reduced by a reductivesubstance to undergo cleavage which causes the release of a mobile dye.This compound is particularly useful in the present invention. ##STR22##wherein Dye represents a group providing a compound which serves as amobile dye after being reduced; and R¹, R², EAG, Time, t, N, X, brokenlines, and solid lines have the same meanings as defined in the generalformula (II). There may be more preferably used a compound representedby the general formula (CIII): ##STR23## wherein Dye is as defined inthe general formula (CII); and the others are as defined in the generalformula (II).

There may be particularly preferably, used a compound represented by thegeneral formula (CIV): ##STR24## wherein Dye is as defined in thegeneral formula (CII); and Y is as defined in the general formula (III).R⁵ and R⁶ each represents a hydrogen atom or substitutable group. R⁵ andR⁶ may be bonded to each other to form a saturated or unsaturated carbonring or heterocyclic group.

Preferred examples of R⁵ include a hydrogen atom; a substituted orunsubstituted alkyl group, such as a methyl group, an ethyl group, at-butyl group, an octadecyl group, a phenethyl group, and acarboxymethyl group; a substituted or unsubstituted aryl group, such asa phenyl group, a 3-nitrophenyl group, a 4-methoxyphenyl group, a4-acetylaminophenyl group, a 4-methanesulfonylphenyl group, a2,4-dimethylphenyl group, a 4-tetradecyloxyphenyl group, and a ##STR25##group; and a substituted or unsubstituted heterocyclic group, such as a2-pyridyl group, a 2-furyl group, and a 3-pyridyl group.

Preferred examples of R⁶ include a hydrogen atom; a substituted orunsubstituted alkyl group, such as a methyl group; a hydroxymethylgroup, and a --CH₂ --(Time--_(t) Dye group; a substituted orunsubstituted aryl group, such as a phenyl group, a 4-chlorophenylgroup, a 2-methylphenyl group, a ##STR26## group, and a ##STR27## group;and a substituted or unsubstituted heterocyclic group, such as a4-pyridyl group.

Examples of R⁵ and R⁶ which together form a fused ring include:##STR28##

Examples of dyes represented by Dye in the general formula (CI) includeazo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes,styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, andphthalocyanine dyes. These dyes can be used in the form of havingtemporarily shorter wavelengths, the color of which is recoverable inthe development processing.

More specifically, the dyes as described in European Patent 76,492A andJapanese Patent Application (OPI) No. 165054/84 can be utilized.

Specific examples of dye providing substance which can be used in thepresent invention will be shown here inafter, but the present inventionshould not be construed as being limited thereto. ##STR29##

The amount of the dye providing substance to be used depends on theabsorption coefficient of the dye and is generally in the range of 0.05to 5 mmol/m², preferably 0.1 to 3 mmol/m². Such a dye providingsubstance may be used singly or in combination with other such dyeproviding substances.

In the present invention, a reductive substance may be used. Thereductive substance may be incorporated in a processing solution fromthe outside of the present color light-sensitive material, or may bepreviously incorporated in the light-sensitive material. Alternatively,the same or different types of reductive substances may be incorporatedin a processing solution while another reductive substance is previouslyincorporated in the light-sensitive material.

The reductive substance may be either an inorganic compound or anorganic compound and its oxidation potential is preferably lower thanthe standard oxidation-reduction potential of silver ion/silver (0.8V).

Examples of such inorganic reductive substances include metals having anoxidation potential of 0.80V or less, such as Mn, Ti, Si, Zn, Cr, Fe,Co, Mo, Sn, Pb, W, H₂, Sb, Cu, and Hg; ions or complex compounds thereofhaving an oxidation potential of 0.8V or less, such as Cr²⁺, V²⁺, Cu⁺,Fe²⁺, MnO₄ ²⁻, I⁻, Co(CN)₆ ⁴⁻, Fe(CN)₆ ⁴⁻, and (Fe-EDTA)²⁻ ;hydrogenated metals having an oxidation potential of 0.8 V or less, suchas NaH, LiH, KH, NaBH₄, LiBH₄, LiAl(O--t--C₄ H₉)₃ H, and LiAl(OCH₃)₃ H;and sulfur or phosphorus compounds having an oxidation potential of 0.8V or less, such as Na₂ SO₃, NaHS, NaHSO₃, H₃ P, H₂ S, Na₂ S, and Na₂ S₂.

As reductive substances of organic compound there may be used organicnitrogen compounds, such as alkylamines and arylamines; organic sulfurcompounds such as alkylmercaptans and arylmercaptans; ororganophosphorus compounds, such as alkylphosphines and arylphosphines.Particularly, a silver halide reductive agent according to Kendal-Pelzequation described in James, The Theory of the Photographic Process (4thedition, p. 299 (1977)) can preferably be used.

Preferred examples of such reductive agents include 3-pyrazolidones andprecursors thereof, such as 1-phenyl-3-pyrazolidone,1-phenyl-4,4-dimethyl-3-pyrazolidone,4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone,1-m-tolyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone,1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone,1-phenyl-4,4-bis(hydroxymethyl)-3-pyrazolidone,1,4-di-methyl-3-pyrazolidone, 4-methyl 3-pyrazolidone,4,4-dimethyl-3-pyrazolidone, 1-(3-chlorophenyl)-4-methyl-3-pyrazolidone,1-(4-chlorophenyl)-4-methyl-3-pyrazolidone,1-(4-tolyl)-4-methyl-3-pyrazolidone,1-(2-tolyl)-4-methyl-3-pyrazolidone, 1-(4-tolyl)-3-pyrazolidone,1-(3-tolyl)- 3-pyrazolidone, 1-(3-tolyl)-4,4-dimethyl-3-pyrazolidone,1-(2-trifluoroethyl)-4,4-dimethyl-3-pyrazolidone,5-methyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone,1-phenyl-4-methyl-4-stearoyloxymethyl 3-pyrazolidone,1-phenyl-4-methyl-4-lauroyloxymethyl-3-pyrazolidone,1-phenyl-4,4-bis(lauroyloxymethyl)-3-pyrazolidone,1-phenyl-2-acetyl-3-pyrazolidone, and 1-phenyl-3-acetoxypyrazolidon; andhydroquinones and precursors thereof, such as hydroquinone,trihydroquinone, 2,6-dimethylhydroquinone, t-butylhydroquinone,2,5-di-t-butylhydroquinone, t-octylhydroquinone,2,5-di-t-octylhydroquinone, pentadecylhydroquinone, sodium5-pentadecylhydroquinone-2-sulfonate, p-benzoyloxyphenol,2-methyl-4-benzoyloxyphenol, and 2-t-butyl-4-(4-chlorobenzoyloxy)phenol.

Other useful examples of silver halide reductive agents include a colordeveloping agent such as a p-phenylene color developing agent, e.g.N,N-diethyl-3-methyl-p-phenylenediamine as described in U.S. Pat. No.3,531,286. Examples of reductive agents which can be more preferablyused include aminophenols as described in U.S. Pat. No. 3,761,270.Particularly preferred among such aminophenol reductive agents are4-amino-2,6-dibromophenol, 4-amino-2,6-dibromophenol,4-amino-2-methylphenol sulfate, 4-amino-3-methylphenol sulfate, and4-amino-2,6-dichlorophenol hydrochloride. Other useful examples of suchreductive agents include 2,6-dichloro-4-substituted sulfoamidophenols,and 2,6-dibromo-4-substituted sulfoamidophenols as described in ResearchDisclosure, No. 15108 and U.S. Pat. No. 4,021,240; andp-(N,N-dialkylphenyl)sulfamines as described in Japanese PatentApplication (OPI) No. 116740/84. Besides the above described phenolicreductive agents there may be used naphtholic reductive agents,particularly 4-amino-naphthol derivatives and 4-substitutedsulfoamidonaphthol derivatives as described in Japanese PatentApplication (OPI) No. 259253/86. Further examples of general colordeveloping agents which can be used in the present invention includeaminohydroxypyrazole derivatives as described in U.S. Pat. No.2,895,825, aminopyrazoline derivatives as described in U.S. Pat. No.2,892,714, and hydrazone derivatives as described in ResearchDisclosure, Nos. 19412 and 19415 (June 1980, pp. 227-230, pp. 236-240).These color developing agents may be used singly or in combination.

If a nondiffusible reductive substance is incorporated in thelight-sensitive material, an electron transfer agent (ETA) may bepreferably used in combination with the reductive substance in order toaccelerate the transfer of electrons between the reductive substance andthe developable silver halide emulsion.

Such an electron transfer agent can be selected among the abovedescribed reductive substances. Such as electron transfer agentpreferably has a higher mobility than an immobile reductive substance inorder to provide a better effect. In this case, as a reductive substanceto be used in combination with ETA there can be used any one of theabove described reductive agents which substantially doesn't move in thelayer of light-sensitive material. Particularly preferred examples ofsuch reductive agents include hydroquinones, aminophenols,aminonaphthols, 3-pyrazolidinones, saccharine and precursors thereof,picoliniums, and compounds as described as electron donors in JapanesePatent Application (OPI) No. 110827/78.

As ETA to be used in combination with these compounds there can be usedany ETA whose oxide can undergo cross oxidation with these compounds.Preferred examples of such ETA include diffusible 3-pyrazolidinones,aminophenols, phenylenediamines, and reductones.

The present color light-sensitive material can be used as a so-calledconventional color diffusion transfer light-sensitive material which isdeveloped with a developing solution at near normal temperature or as aheat-developable color light-sensitive material.

If the color light-sensitive material of the present invention isapplied to such a conventional color diffusion transfer light-sensitivematerial, the above described reductive substance or a combination ofsuch a reductive substance and ETA may be preferably allowed to act onthe light-sensitive material by supplying it to the light-sensitivematerial in the form of a developing solution during the development orby supplying ETA to the light-sensitive material in the form of adeveloping solution with the reductive substance incorporated in thelight-sensitive material. In the former process, the amount of thereductive substance and/or ETA to be used is 0.001 to 1 mol per mol ofthe total solution. In the latter process, the amount of the reductivesubstance and ETA to be used are preferably 0.01 to 50 mols per mol ofdye providing substance and 0.001 to 1 mol per liter of the totalsolution, respectively.

On the other hand, if the present color light-sensitive material isapplied to a heat-developable color light-sensitive material, thereductive substance or a combination of such a reductive substance andETA is preferably incorporated in the heat-developable colorlight-sensitive material. In this case, the amount of the reductivesubstance to be used is 0.01 to 50 mols, preferably 0.1 to 5 mols of dyeproviding substance, or 0.001 to 5 mols, preferably 0.01 to 1.5 mols,per mol of silver halide.

The incorporation of the above described development inhibitorprecursor, dye providing compound, and other hydrophobic additives inthe layer of light-sensitive element can be accomplished by any suitablemethods as described in U.S. Pat. No. 2,332,027. In this process, a highboiling organic solvent as described in Japanese Patent Application(OPI) Nos. 83154/84, 178451/84, 178452/84, 178453/84, 178454/84,178455/84, and 178457/84 can be optionally used in combination with alow boiling organic solvent having a boiling point of 50° to 160° C.

The amount of such a high boiling organic solvent to be used is 10 g orless, preferably 5 g or less, per gram of dye providing substance.

Alternatively, a dispersion process using a polymer as described inJapanese Patent Publication No. 39853/76 and Japanese Patent Application(OPI) No. 59943/76 can be used.

If the compound to be dispersed in the light-sensitive element is asubstantially water-insoluble compound, it can be dispersed in thelight-sensitive material by dispersing finely divided particles of thecompound in a binder and then incorporating the binder in thelight-sensitive material.

If a hydrophobic substance is dispersed in a hydrophilic colloid, it canbe accomplished with various surface active agents. For example, surfaceactive agents as described in Japanese Patent Application (OPI) No.157636/84 can be used.

As suitable silver halide for the present color light-sensitive materialthere may be used silver chloride, silver bromide, silver bromochloride,silver iodochloride, or silver bromoiodochloride.

More specifically, any silver halide emulsions as described in U.S. Pat.No. 4,500,626, Research Disclosure, No. 17029 (June 1978, pp. 9-10), andJapanese Patent Application (OPI) Nos. 107240/86, 85241/87, and 87957/87can be used.

The silver halide emulsion to be used in the present invention may be ofthe surface latent image type in which latent images are formed mainlyin the surface thereof or the internal latent image type in which latentimages are formed mainly in the interior thereof. The present silverhalide emulsion may be a so-called core shell emulsion having differentphases from the interior to the surface of the grains. In the presentinvention, a direct reversal emulsion comprising a combination of aninternal latent image type emulsion and a nucleating agent can be used.

The silver halide emulsion may be used unripened but is normally usedafter being chemically sensitized. An emulsion for ordinary typelight-sensitive material can be sensitized by a known sulfur sensitizingprocess, reduction sensitizing process, or noble metal sensitizingprocess, or a combination thereof. These chemical sensitizing processesmay be effected in the presence of a nitrogen-containing heterocycliccompound as described in Japanese Patent Application (OPI) Nos.126526/83 and 215644/83.

The coated amount of the present light-sensitive silver halide is 1 mgto 10 g/m² in terms of silver.

The silver halide to be used in the present invention may be spectrallysensitized with methine dyes or other dyes. Examples of such dyes whichcan be used in the spectral sensitization include cyanine dyes, melocyanine dyes, complex cyanine dyes, complex melocyanine dyes, holopolarcyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.

More specifically, sensitizing dyes as described in Japanese PatentApplication (OPI) Nos. 180550/84 and 140335/85 and Research Disclosure,No. 17029 (June 1978, pp. 12-13), and heat-decolorable sensitizing dyesas described in Japanese Patent Application (OPI) Nos. 111239/85 and32446/87 may be used.

These sensitizing dyes can be used singly or in combination. Acombination of sensitizing dyes is particularly useful for the purposeof supersensitization.

A dye which itself doesn't have a spectral sensitizing effect orsupersensitizing substance which doesn't substantially absorb visiblelight may be incorporated in the emulsion together with such asensitizing dye. Examples of such a dye or supersensitizing substanceare described in U.S. Pat. Nos. 2,933,390, 3,635,721, 3,743,510,3,615,613, 3,615,641, 3,617,295, and 3,635,721.

These sensitizing dyes can be added to the emulsion during or before orafter the chemical ripening Alternatively, these sensitizing dyes can beadded to the emulsion before or after the formation of particulatesilver halide as described in U.S. Pat. Nos. 4,183,756 and 4,225,666.

The added amount of the sensitizing dye is normally in the range of 10⁻⁵to 10⁻² mol per mol of silver halide.

The present color light-sensitive material may be provided on adifferent support from the image-receiving element (dye fixing element)or a film unit combined with the image-receiving element.

In a typical embodiment of film unit, the above describedimage-receiving element and light-sensitive element are laminated on atransparent support so that the light-sensitive element doesn't need tobe peeled off the image-receiving element after the completion of atransferred image. More specifically, the image-receiving elementcomprises at least one mordant layer. A preferred embodiment of thelight-sensitive element may comprise a combination of a blue-sensitiveemulsion layer, a green-sensitive emulsion layer, and a red-sensitiveemulsion layer; a combination of a green-sensitive emulsion layer, ared-sensitive emulsion layer, and an infrared-sensitive emulsion layer;or a combination of a blue-sensitive emulsion layer, a red-sensitiveemulsion layer, and an infrared-sensitive emulsion layer, with therespective emulsion layers combined with a yellow dye providingsubstance, a magenta dye providing substance, and a cyan dye providingsubstance, respectively. (The term "infrared-sensitive emulsion layer"as used herein means an emulsion layer having a light-sensitivity tolight of wavelength of 700 nm or more, particularly 740 nm or more).Furthermore, a white reflecting layer containing a solid pigment such astitanium oxide may be provided between the mordant layer and thelight-sensitive layer or the dye providing substance-containing layer sothat a transferred image can be observed through the transparentsupport. A light-shielding layer may be further provided between thewhite reflecting layer and the light-sensitive layer so that thedevelopment processing can be conducted in a light place. A peel-apartlayer may be optionally provided in a proper location so that thelight-sensitive element can be entirely or partially peeled off theimage receiving element. Such an embodiment is described in JapanesePatent Application (OPI) No. 67840/81 and Canadian Patent 674,082.

Another embodiment which doesn't need peeling may comprise the abovedescribed light-sensitive element coated on a transparent support, awhite reflecting layer coated thereon, and an image-receiving layerlaminated thereon. An embodiment which comprises a lamination of animage-receiving element, a white reflecting layer, a peel-apart layer,and a light-sensitive element on the same support so that thelight-sensitive element can be intentionally peeled off theimage-receiving element is described in U.S. Pat. No. 3,730,718. On theother hand, a construction comprising a light-sensitive element and animage-receiving element separately coated on two supports can be roughlydivided into two typical embodiments, i.e. peel-apart type andnon-peeling type. More specifically, a preferred embodiment ofpeel-apart type film unit comprises a light-reflecting layer provided onthe back side of a support, the surface of the light-reflecting layerhaving at least one image-receiving layer coated thereon. Alight-sensitive element is coated on a support having a light-shieldinglayer. In this arrangement, the light-sensitive layer-coated surface andthe mordant layer-coated surface are not opposed to each other beforeexposure, but the light-sensitive layer-coated surface is turned over sothat it is opposed to the image-receiving layer-coated surface afterexposure (e.g., during development). After a transferred image iscompleted on the mordant layer, the light-sensitive element can besmoothly peeled off the image-receiving element.

A preferred embodiment of non-peeling film unit may comprise at leastone mordant layer coated on a transparent support, and a light-sensitiveelement coated on a transparent support or support having alight-shielding layer, the light-sensitive layer-coated surface and themordant layer-coated surface being opposed to each other.

The above two embodiments can be all applied to the color diffusiontransfer process or heat development process. Particularly, in theformer embodiment, a pressure-rupturable container (processing element)containing an alkaline processing solution may be provided. In anon-peeling film unit comprising an image-receiving element and alight-sensitive element laminated on a support, such a processingelement is preferably provided between the light-sensitive element and acover sheet superimposed thereon. In an embodiment comprising alight-sensitive element and an image-receiving element comprising alight-sensitive element and an image-receiving element separately coatedon two supports, the processing element is preferably provided betweenthe light-sensitive element and the image-receiving element at latestduring development. Such a processing element preferably comprises alight-shielding layer (carbon black, or a dye which changes color undersome pH condition) and/or white pigment (e.g., titanium oxide) dependingon the embodiment of the film unit. In the film unit for color diffusiontransfer process, a neutralization timing mechanism comprising acombination of a neutralization layer and a neutralization timing layermay be preferably incorporated in the cover sheet, image-receivingelement, or light-sensitive element.

On the other hand, in a film unit for a heat development process, aheating layer containing electrically conductive fine particles ofmetal, carbon black, graphite, or the like may be provided in a properposition in the support, light-sensitive element, or image-receivingelement so that Joules heat produced upon passage of electric currentcan be used for heat development or transfer of dye. Such electricallyconductive particles can be replaced by semi-conductive inorganicmaterials such as silicon carbide, molybdenum silicate, lanthanumchloride, barium titanate ceramics, tin oxide, and zinc oxide.

The present invention will be further described with reference to thecase where the present invention is applied to a heat-developable colorlight-sensitive material.

If the present invention is applied to a heat-developable colorlight-sensitive material, an organic metal salt may be used as anoxidizing agent together with silver halide. In this case, it isnecessary that the light-sensitive silver halide and the organic metalsalt be in contact with or in adjacent to each other.

Particularly preferred among these organic metal salts are organicsilver salts.

As organic compounds to be used for the formation of the above describedorganic silver salt oxidizing agent there can be used compounds asdescribed in Japanese Patent Application (OPI) No. 107240/86 and U.S.Pat. No. 4,500,626. Other useful examples of such compounds includesilver salts of carboxylic acid containing an alkynyl group such assilver phenylpropiolate as described in Japanese Patent Application(OPI) No. 231542/86, and acetylene silver as described in JapanesePatent Application (OPI) No. 249044/86. These organic silver salts maybe used in combination.

The amount of the above described organic silver salt to be used isnormally in the range of 0.01 to 10 mols, preferably 0.01 to 1 mol, permol of light-sensitive silver halide. The total coated amount of thelight-sensitive halide and the organic silver salt is 50 mg to 10 g/m²in terms of silver.

In the present invention, a compound which serves to both activatedevelopment and stabilize images can be used. Specific examples of sucha compound which can be preferably used in the present invention aredescribed in U.S. Pat. No. 4,500,626.

In the present invention, various anti-foggants or photographicstabilizers can be used. Examples of such anti-foggants or photographicstabilizers which can be used in the present invention include azolesand azaindenes as described in Resent Disclosure (Dec. 1978, pp. 24 to25), carboxylic acids and phosphoric acids containing nitrogen atoms asdescribed in Japanese Patent Application (OPI) No. 168442/84, mercaptocompounds and metal salts thereof as described in Japanese PatentApplication (OPI) No. 111636/84, and acetylene compounds as described inJapanese Patent Application (OPI) No. 228267/85.

The present color light-sensitive material may optionally comprisevarious conventional additives for heat-developable light-sensitivematerial, or layers in addition to the light-sensitive layer such asprotective layer, interlayer, anti-static layer, anti-halation layer,peel-apart layer for facilitating peeling from the dye fixing element,and matting layer. Examples of such various conventional additivesinclude plasticizers, matting agents, sharpness improving dyes,antihalation dyes, surfacer active agents, fluorescent brighteningagents, anti-slip agents, antioxidants, and anti-fading agents asdescribed in Research Disclosure (June 1978, pp. 9 to 15) and JapanesePatent Application (OPI) No. 88256/86.

Particularly, the protective layer may normally contain an organic orinorganic matting agent to inhibit adhesion. The protective layer mayalso contain a mordant or ultraviolet light absorber. The protectivelayer and the interlayer each may consist of two or more layers.

The interlayer may also contain a reductive agent for inhibiting colorfading or color stain, an ultraviolet light absorber, or a white pigmentsuch as titanium dioxide. Such a white pigment may be incorporated inthe emulsion layer besides the interlayer to improve sensitivity.

The image-receiving element (hereinafter referred to as "dye fixingelement") may optionally comprise a protective layer, a peel-apartlayer, an anticurl layer, or other auxiliary layers. Particularly, sucha protective layer may be effectively provided. One or more of the abovedescribed layers may optionally contain a hydrophilic heat solvent, aplasticizer, an anti-fading agent, an ultraviolet light absorber, alubricant, a matting agent, an antioxidant, a dispersed vinyl compoundfor increasing dimensional stability, a surface active agent, afluorescent brightening agent, or the like. Particularly, in a systemwhere heat development and dye transfer are simultaneously effected inthe presence of a small amount of water, the dye fixing element maypreferably contain a base and/or base precursor described later toimprove the preservability of the light-sensitive element. Specificexamples of these additives are described in Japanese Patent Application(OPI) No. 88256/86.

The light-sensitive element and/or dye fixing element in a heatdevelopable color light-sensitive material may comprise an imageformation accelerator. Such an image formation accelerator can serve toaccelerate oxidation-reduction reaction of a silver salt oxidizing agentwith a reductive agent, production or decomposition of a dye or releaseof a diffusible dye from a dye providing substance, and transfer of adye from a light-sensitive material layer to a dye fixing layer. Fromthe standpoint of physicochemical function, such an image formationaccelerator has many categories such as base or base precursor,nucleophilic compound, high boiling organic solvent (oil), heat solvent,surface active agent, and compound capable of interacting with silver orsilver ion. However, these substance groups normally have a compositefunction and thus have a plurality of the above described accelerationeffects. This is further described in Japanese Patent Application (OPI)No. 93451/86.

There are various methods for generating a base. Compounds which can beused in these methods can be effectively used as base precursors.Examples of such methods include a method described in Japanese PatentApplication (OPI) No. 169585/85 which comprises mixing a difficultlysoluble metal compound with a compound capable of complexing with metalions constituting said difficultly soluble metal compound (complexingcompound) to generate a base, and a method described in Japanese PatentApplication (OPI) No. 232451/86 which comprises electrolysis to generatea base.

Particularly, the former method may be effectively used. Examples ofsuch a difficultly soluble metal compound, include carbonate, hydroxide,and oxide of zinc, aluminum, calcium, and barium. Such a complexingcompound is further illustrated in A. E. Martell and R. M. Smith,Critical Stability Constants (Vol. 4 and Vol. 5, Plenum Press). Specificexamples of such a complexing compound include salts of aminocarboxylicacids, iminodiacetic acids, pyridylcarboxylic acids, aminophosphoricacids, carboxylic acids (such as monocarboxylic acids, dicarboxylicacids, tricarboxylic acids, tetracarboxylic acids, and compoundscontaining substituents such as phosphono group, hydroxyl group, oxogroup, ester group, amido group, alkoxy group, mercapto group, alkylthiogroup, and phosphino group), hydroxamic acids, polyacrylates, andpolyphosphoric acids with alkali metals, guanidines, amidines, orquaternary ammonium salts.

The difficultly soluble metal compound and the complexing compound maybe preferably separately incorporated in the light-sensitive element andthe dye fixing element.

The light-sensitive element and/or the dye fixing element in a heatdevelopable color light-sensitive material may comprise variousdevelopment stop agents for the purpose of obtaining constant imagesagainst fluctuations in processing temperature and processing timeduring development.

The term "development stop agent" as used herein means a compound whichrapidly neutralizes or reacts with a base after proper development toreduce the base density in the film to stop development or a compoundwhich interacts with silver or silver salts to inhibit development.Specific examples of such a development stop agent include acidprecursors which release an acid upon heating, electrophilic compoundswhich undergo displacement reaction with a coexisting base upon heating,and nitrogen-containing heterocyclic compounds, mercapto compounds, andprecursors thereof as described in Japanese Patent Application (OPI)Nos. 108837/85, 192939/85, 230133/85, and 230134/85.

As suitable development stop agents there also may be effectively usedcompounds which release a mercapto compound upon heating. Specificexamples are those described in Japanese Patent Application (OPI) Nos.67851/86, 147244/86, 12494/86, 185743/86, 182039/86, 185744/86,184539/86, 188549/86, and 53632/86.

As a binder for the light-sensitive element and/or dye fixing element ina heat developable color light-sensitive material there can be ahydrophilic binder. A typical example of such a hydrophilic binder is atransparent or semi-translucent hydrophilic binder. Examples of such ahydrophilic binder include proteins such as gelatin and gelatinderivative; natural substances such as starch, gum arabic, and otherpolysaccharides; and synthetic polymerized substances such as polyvinylpyrrolidone, acrylamide polymer, and other water-soluble polyvinylcompounds. Other examples of hydrophilic binders which can be used inthe present invention include a dispersed vinyl compound for increasingthe dimensional stability of a photographic material. Such a dispersedvinyl compound is normally used in the form of a latex. These bindersmay be used singly or in combination.

In the present invention, the coated amount of the binder is 20 g orless, preferably 10 g or less, particularly 7 g or less, per m².

The amount of the high boiling solvent to be dispersed in the bindertogether with a hydrophobic compound such as dye providing substance is1 cc to less, more preferably 0.5 cc or less, particularly 0.3 cc orless, per g of binder.

The layers constituting the light-sensitive element and/or dye fixingelement (photographic emulsion layer, dye fixing layer, etc.) mayoptionally contain an organic or inorganic film hardener.

Specific examples of such a film hardener are described in JapanesePatent Application (OPI) Nos. 147244/86 and 157636/84. These filmhardeners may be used singly or in combination.

In order to accelerate the transfer of a dye, a hydrophilic heat solventwhich stays solid at room temperature but becomes soluble at an elevatedtemperature may be incorporated in the light-sensitive element or dyefixing element. Such a hydrophilic heat solvent may be incorporated ineither or both of the light-sensitive element and the dye fixingelement. In the light-sensitive element or dye fixing element, such ahydrophilic heat solvent may be incorporated in any one of the emulsionlayer, interlayer, protective layer, and dye fixing layer. Preferably,such a heat solvent may be incorporated in the dye fixing layer and/oradjacent layers thereto. Examples of such a hydrophilic heat solventinclude ureas, pyridines, amides, sulfonamides, imides, alcohols,oximes, and other heterocycles. In order to accelerate the transfer of adye, a high boiling organic solvent may be incorporated in thelight-sensitive element and/or dye fixing element.

The support to be used for the light sensitive element and/or dye fixingelement must be able to withstand the processing temperature. Ingeneral, suitable supports can be glass, paper, polymer film, metal, andanalogous materials thereto. Other examples of such supports includethose described as supports in Japanese Patent Application (OPI) No.147244/86.

In an embodiment, the light-sensitive element and/or dye fixing elementmay comprise an electrically conductive heating element layer as aheating means for heat development or dye diffusion transfer.

In this case, such a transparent or opaque heating element can beprepared as a heating resistor by any suitable known methods. As such aheating resistor there may be used a thin film of inorganic materialshowing semi-conductivity or an inorganic thin film containing anelectrically conductive particles dispersed therein. Examples ofmaterials which can be used to prepare such a heating resistor are thosedescribed in Japanese Patent Application (OPI) No. 29835/86.

The coating of heat developable light-sensitive layer, protective layer,interlayer, subbing layer, back layer, dye fixing layer, and otherlayers can be accomplished by any suitable methods as described in U.S.Pat. No. 4,500,626.

As sources of light for imagewise exposure to record images on thelight-sensitive element there can be used radiant sources emittingvisible light or other rays. In general, light sources commonly used forordinary color print can be used. Examples of such light sources includetungsten lamp, mercury vapor lamp, halogen vapor lamp such as iodinevapor lamp, xenon vapor lamp, laser source, CRT source, light-emittingdiode, and other light sources as described in Japanese PatentApplication (OPI) No. 147244/86 and U.S. Pat. No. 4,500,626.

The heat development step and the dye transfer step may be separately orsimultaneously effected. Alternatively, the two steps may besequentially effected. That is, the development step may be followed bythe dye transfer step in a process.

For example, in one process, a light-sensitive element is imagewiseexposed to light and heated. A dye fixing element is then superimposedon the light sensitive element. If necessary, the laminate is heated sothat a mobile dye is transferred to the dye fixing element. In anotherprocess, a light-sensitive element is imagewise exposed to light. A dyefixing element is superimposed on the light sensitive element andheated. These two processes may be effected in an environmentsubstantially free of water or in the presence of a slight amount ofwater.

In the heat development step, development can be accomplished by aheating temperature of about 18° C. to about 80° C., particularly about25° C. to about 50° C. In the case where heat development is effected inthe presence of a slight amount of water, the upper limit of heatingtemperature is not higher than the boiling point of the material. In thecase where the transfer step is effected after the completion of theheat development step, transfer can be accomplished by a heatingtemperature in the range of the heating temperature at the heatdevelopment step to room temperature, preferably between 50° C. and thetemperature about 10° C. lower than the heating temperature at the heatdevelopment step.

A preferred method for forming images comprises heating alight-sensitive material in the presence of a slight amount of water anda base and/or base precursor after or at the same time with imagewiseexposure, and then transferring to a dye fixing layer a diffusible dyeproduced at portions counter-corresponding to silver images at the sametime with development. In accordance with this process, the productionor release of a diffusible dye proceeds at an extremely high reactionrate, accelerating the transfer of the diffusible dye to the dye fixinglayer. This can provide a high density color image in a short period oftime.

The amount of water to be used for wet-heat development in thisembodiment may be as small as at least 0.1 time, preferably 0.1 or moretimes by weight the weight of total coated amount of the light-sensitiveelement and the dye fixing element but not more than the weight of thesolvent corresponding to the maximum wet volume of the whole film coated(particularly not higher than the amount obtaining subtracting theweight of the whole film coated from the weight of the solventcorresponding to the maximum wet volume of the whole film coated).

The film becomes unstable when wet. Thus, the film can show local stainunder some conditions. In order to avoid such a problem, the amount ofwater to be used in this embodiment is preferably as much as the wetvolume of the total coated film of the light-sensitive element and thedye fixing element or less. More specifically, the amount of water to beused is 1 to 50 g, preferably 2 to 35 g, particularly 3 to 25 g, per m²of the total area of the light-sensitive element and the dye fixingelement.

The base and/or base precursor to be used in this embodiment may beincorporated in the light-sensitive element or the dye fixing element.The base or base precursor may be supplied in the form of an aqueoussolution.

In the above described embodiment, the image formation reaction systemmay preferably contain as base precursors a difficultly water solublebasic metal compound and a compound capable of complexing metal ionsconstituting the difficultly water-insoluble metal compound with wateras a medium so that the reaction of the two compounds upon heatingraises the pH value of the system. The term "image formation reactionsystem" as used herein means a region where an image formation reactionoccurs. Specific examples of such a system include a layer belonging toboth the light-sensitive element and the dye fixing element. In the casewhere two or more layers exist, any of these layers can be such asystem.

The difficultly soluble metal compound and the complexing compound needto be incorporated in at least separate layers to prevent reactionbefore development. For example, in a so-called monosheet material inwhich a light-sensitive element and a dye fixing element are provided onthe same support, the two compounds are preferably incorporated inseparate layers with another layer interposed therebetween. In a morepreferred embodiment, a difficultly soluble metal compound and acomplexing compound are incorporated in layers provided on separatesupports For example, the difficultly soluble metal compound isincorporated in a light-sensitive element while the complexing compoundis incorporated in a dye fixing element comprising a different supportfrom that of the light-sensitive element. The complexing compound may besupplied in the form of a solution in the coexisting water. Such adifficultly soluble metal compound is preferably incorporated in theelement in the form of a dispersion of finely divided particles preparedby a suitable method as described in Japanese Patent Application (OPI)Nos. 174830/81 and 102733/78. The average particle size of such finelydivided particles of difficultly soluble metal compound is 50 μm orless, preferably 5 μm or less. Such a difficultly soluble metal compoundmay be incorporated in any layer selected from light-sensitive layer,interlayer, and protective layer in the light-sensitive element.Alternatively, such a difficultly soluble metal compound may beincorporated separately in two or more layers.

The amount of the difficultly soluble metal compound or the complexingcompound to be incorporated in the layers above the support depends onthe type of compound to be used, the particle size of the difficultlysoluble compound, the complexing reaction rate, or the like but isnormally in the range of 50% by weight or less, preferably 0.01 to 40%by weight, in terms of weight of coated film. In the case where thecomplexing compound is supplied in the form of an aqueous solution, itsconcentration is preferably in the range of 0.005 to 5 mols,particularly 0.05 to 2 mols, per liter. Furthermore, the amount of thecomplexing compound to be incorporated in the present reaction system ispreferably 1/100 to 100 times, particularly 1/10 to 20 times, that ofthe difficultly soluble compound by molar ratio.

The incorporation of water in the light-sensitive layer or dye fixinglayer can be accomplished by any suitable method as described inJapanese Patent Application (OPI) No. 147244/86.

As heating means for development and/or transfer process there may beused a heating plate, an iron, a heating roller, and the like asdescribed in Japanese Patent Application (OPI) No. 147244/86.Furthermore, the light-sensitive element and/or dye fixing element maybe laminated with an electrically conductive material layer of graphite,carbon black, metal, or the like. In such an arrangement, direct heatingcan be accomplished by passing an electric current through theelectrically conductive layer.

The pressure conditions for close adhesion of the light-sensitiveelement and the dye fixing element and methods for applying pressure tosuch a laminate are described in Japanese Patent Application (OPI) No.147244/86.

The processing of the present heat developable color light-sensitivematerial can be accomplished by any suitable heat developing device asdescribed in Japanese Patent Application (OPI) Nos. 75247/84, 177547/84,181353/84, and 18951/85, and Japanese Utility Model Application (OPI)No. 25942/87.

The present invention will be further illustrated in the followingexamples, but the present invention should not be construed as beinglimited thereto.

EXAMPLE 1

The preparation of an emulsion for 1st layer will be describedhereinafter.

600 ml of an aqueous solution containing sodium chloride and potassiumbromide and an aqueous solution of nitric acid which had been preparedby dissolving 0.59 mol of silver nitrate in 600 ml of water were addedat the same time to a well stirred aqueous solution of gelatin which hadbeen prepared by dissolving 20 g of gelatin and 3 g of sodium chloridein 1,000 ml of water and kept at a temperature of 75° C. for 40 minutesat the same flow rates. As a result, a monodisperse emulsion of cubicparticulate silver bromochloride having an average grain size of 0.35 μm(bromine: 80 mol %) wa obtained.

The emulsion thus obtained was then washed with water and desalted. 5 mgof sodium thiosulfate and 20 mg of4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene were added to the emulsionthus processed. The emulsion was then chemically sensitized at atemperature of 60° C. The yield of the desired emulsion was 600 g.

The preparation of an emulsion for the 3rd layer will be describedhereinafter.

600 ml of an aqueous solution containing sodium chloride and potassiumbromide, an aqueous solution of silver nitrate which had been preparedby dissolving 0.59 mol of silver nitrate in 600 ml of water, and a dyesolution (I) described hereinafter were added at the same flow rates atthe same time to a well stirred aqueous solution which had been preparedby dissolving 20 g of gelatin and 3 g of sodium chloride in 1,000 ml ofwater and kept at a temperature of 75° C. for 40 minutes. As a result, amonodisperse emulsion of dye-adsorbed cubic particulate silverbromochloride having an average grain size of 0.35 μm (bromine: 80 mol%) was obtained.

The emulsion thus obtained was then washed with water and desalted. 5 mgof sodium thiosulfate and 20 mg of4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene were added to the emulsionthus processed. The emulsion was chemically sensitized at a temperatureof 60° C. The yield of the desired emulsion was 600 g.

    __________________________________________________________________________    Dye Solution (I)                                                              __________________________________________________________________________     ##STR30##                             160 mg                                 Methanol                               400 ml                                 __________________________________________________________________________

The preparation of a silver halide emulsion for 5th layer will bedescribed hereinafter.

1,000 ml of an aqueous solution containing potassium iodide andpotassium bromide and an aqueous solution of silver nitrate which hadbeen prepared by dissolving 1 mol of silver nitrate in 1,000 ml of waterwere added at the same time to a well stirred aqueous solution which hadbeen prepared by dissolving 20 g of gelatin and ammonia in 1,000 ml ofwater and kept at a temperature of 50° C., and the pAg value of thesystem was kept constant. As a result, a monodisperse emulsion ofoctahedral particulate silver bromoiodide having an average grain sizeof 0.5 μm (iodine: 5 mol %) was obtained.

The emulsion thus obtained was then washed with water and desalted. 5 mgof chloroauric acid (tetrahydrate) and 2 mg of sodium thiosulfate wereadded to the emulsion thus processed. The emulsion was subjected to goldand sulfur sensitization at a temperature of 60° C. The yield of thedesired emulsion was 1.0 kg.

The preparation of a gelatin dispersion of a dye providing substancewill be described hereinafter.

18 g of a yellow dye providing substance (1) of the undermentionedstructure, 2.2×10⁻² mol of a reductive substance ED-1, and 9 g of a highboiling solvent (*4) were weighed and combined. 46 ml of cyclohexanonewas added to the admixture. The admixture was then heated to atemperature of about 60° C. to prepare a uniform solution. To thesolution thus obtained, 100 g of a 10% solution of lime-treated gelatinand 1.5 g of sodium dodecylbenzenesulfonate were mixed with stirring.The admixture was then subjected to dispersion by means of a homogenizerat 10,000 rpm for 10 minutes. The dispersion thus obtained is referredto hereafter as a dispersion of a yellow dye providing substance.

A dispersion of a magenta dye providing substance and a dispersion of acyan dye providing substance were similarly prepared from a magenta dyeproviding substance (7) and a cyan dye providing substance (8),respectively.

With these emulsions and dispersions, a multilayer color light-sensitivematerial 101 shown in Table 1 was prepared.

Light-sensitive materials 102 to 105 having the similar constructionwere prepared in the same manner as in the light sensitive material 101except that compounds of the present invention shown in Table 2 wereadded to the 1st layer, 3rd layer, and 5th layer in the light-sensitivematerial 101 in amounts of 0.5 molar time that of the respective dyeproviding substances. ##STR31##

                  TABLE 1                                                         ______________________________________                                        6th Layer:                                                                    Gelatin                 80     mg/m.sup.2                                     Film hardener*.sup.6    100    mg/m.sup.2                                     Silica*                 100    mg/m.sup.2                                     Zinc hydroxide*.sup.7   300    mg/m.sup.2                                     5th Layer: Blue-sensitive emulsion layer                                      Silver bromoiodide emulsion                                                                           500    mg/m.sup.2 as                                  (iodine: 5 mole %)             silver                                         Yellow dye providing substance (1)                                                                    400    mg/m.sup.2                                     Gelatin                 1,000  mg/m.sup.2                                     Electron donor ED-1     277    mg/m.sup.2                                     1,5-Diphenyl-3-pyrazolidone                                                                           60     mg/m.sup.2                                     High boiling solvent*.sup.4                                                                           200    mg/m.sup.2                                     Surface active agent*.sup.2                                                                           100    mg/m.sup.2                                     4th Layer: Interlayer                                                         Gelatin                 800    mg/m.sup.2                                     Zinc hydroxide*.sup.7   300    mg/m.sup.2                                     3rd Layer: Green-sensitive emulsion Layer                                     Silver bromochloride emulsion                                                                         400    mg/m.sup.2 as                                  (bromine: 80 mol %)            silver                                         Magenta dye providing substance (7)                                                                   400    mg/m.sup.2                                     Gelatin                 1,000  mg/m.sup.2                                     Electron donor ED-1     277    mg/m.sup.2                                     1,5-Diphenyl-3-pyrazolidone                                                                           50     mg/m.sup.2                                     High boiling solvent*.sup.4                                                                           200    mg/m.sup.2                                     Surface active agent*.sup.2                                                                           100    mg/m.sup.2                                     2nd Layer: Interlayer                                                         Gelatin                 800    mg/m.sup.2                                     Zinc hydroxide*.sup.7   300    mg/m.sup.2                                     1st Layer: Red-sensitive emulsion layer                                       Silver bromochloride emulsion                                                                         350    mg/m.sup.2 as                                  (bromine: 80 mol %)            silver                                         Sensitizing dye*.sup.3  8      × 10.sup.-7                                                             mol/m.sup.2                                    Cyan dye providing substance (8)                                                                      300    mg/m.sup.2                                     Gelatin                 1,000  mg/m.sup.2                                     Electron donor ED-1     208    mg/m.sup.2                                     1,5-Diphenyl-3-pyrazolidone                                                                           50     mg/m.sup.2                                     High boiling solvent*.sup.4                                                                           150    mg/m.sup.2                                     Surface active agent*.sup.2                                                                           100    mg/m.sup.2                                     Support*.sup.1                                                                ______________________________________                                         *.sup.1 Polyethylene terephthalate (film thickness: 100 μm)                ##STR32##                                                                     ##STR33##                                                                     ##STR34##                                                                     *.sup.5 Size 4 μm                                                          *.sup.6 1,2-Bis(vinyl sulfonylacetamide)ethane                                *.sup.7 Size 0.2 μm                                                   

The preparation of a dye fixing material will be described hereinafter.

63 g of gelatin, 130 g of a mordant of the undermentioned structure, and80 g of guanidine picolate were dissolved in 1,300 ml of water. Thesolution thus obtained was coated on a paper support laminated withpolyethylene in an amount such that the wet film thickness reached 45μm. The film thus coated was then dried. ##STR35##

A solution of 35 g of gelatin and 1.05 g of 1,2-bis(vinylsulfonylacetamide)ethane in 800 ml of water was coated on the film thusobtained in an amount such that the wet film thickness reached 17 μm.The film thus coated was then dried. As a result, a dye fixing materialwas prepared.

The multilayered color light-sensitive material was then exposed to alight of 2,000 lux from a tungsten lamp through blue, green, red, andgrey color separation filters having a density gradation.

The emulsion surface of the light-sensitive material thus exposed wassupplied with 15 ml/m² of water through a wire bar. The light-sensitivematerial was then laminated with the dye fixing material in such amanner that the film surface of the two materials faced each other.

The laminate was heated for 25 seconds by means of a heat roller whosetemperature had been adjusted so as to keep the temperature of thewater-absorbed film at 80° C. The light-sensitive material was thenpeeled off the dye fixing material. As a result, blue, green, red, andgrey sharp images corresponding to the blue, green, red, and grey colorseparation filters, respectively, on the dye fixing material wereobtained.

The maximum density (D_(max)) and the minimum density (D_(min)) of cyan,magenta, and yellow on the grey portion were measured. The results areshown in Table 2.

                  TABLE 2                                                         ______________________________________                                               Pre-                                                                   Light- sent                                                                   sensitive                                                                            Com-    Dmax           Dmin                                            Material                                                                             pound           Ma-              Ma-                                   No.    No.     Yellow  genta Cyan Yellow                                                                              genta Cyan                            ______________________________________                                        101    None    1.50    1.62  1.70 0.26  0.30  0.32                                   (con-                                                                         trol)                                                                  102    AF-3    1.98    2.00  2.20 0.22  0.25  0.26                            103    AF-6    2.01    2.10  2.30 0.21  0.24  0.25                            104    AF-9    2.11    2.20  2.38 0.20  0.23  0.24                            105     AF-36  1.96    2.02  2.18 0.22  0.25  0.26                            ______________________________________                                    

Table 2 shows that the use of the present compounds can provide imageshaving a high density and a low stain.

The analysis of the amount of reduced silver in the unexposed portionson the light-sensitive materials showed that the light-sensitivematerials 102 to 105 were 1/3 or less of the light-sensitive material101 in the amount of reduced silver. It was thus found that the use ofthe present compounds can help release an antifoggant during heatdevelopment, inhibiting development fog.

EXAMPLE 2

Light-sensitive materials 201 and 202 having the same construction asthe light-sensitive materials 101 and 102 were prepared in the samemanner as in the light-sensitive materials 101 and 102 except that thedye providing substances (1), (7), and (8) were replaced by the dyeproviding substances (10), (2), and (13) in the same amounts,respectively. Furthermore, light-sensitive materials 203 and 204 havingthe same construction as the light-sensitive materials 101 and 102 wereprepared in the same manner as in the light-sensitive materials 101 and102 except that the reductive substance ED-1 was replaced by theundermentioned reductive substance ED-2 in the same molar amount,respectively. These light-sensitive materials were then processed withthe dye fixing material in accordance with the same processing step inExample 1 except that heat development and transfer steps were effectedat a temperature of 90° C. for 20 seconds. As a result, photographicproperties shown in Table 3 were obtained. ##STR36##

                  TABLE 3                                                         ______________________________________                                               Pre-                                                                   Light- sent                                                                   sensitive                                                                            Com-    Dmax           Dmin                                            Material                                                                             pound           Ma-              Ma-                                   No.    No.     Yellow  genta Cyan Yellow                                                                              genta Cyan                            ______________________________________                                        201    None    1.52    1.63  1.75 0.25  0.29  0.29                                   (con-                                                                         trol)                                                                  202    AF-3    2.05    2.20  2.39 0.20  0.20  0.24                            203    None    1.40    1.52  1.69 0.28  0.31  0.32                                   (con-                                                                         trol)                                                                  204    AF-3    1.93    2.06  2.16 0.21  0.23  0.23                            ______________________________________                                    

Table 3 shows that the light-sensitive materials comprising the presentcompounds provide an image having a high density and a low stain.

EXAMPLE 3

A color light-sensitive material 301 shown in Table 4 was prepared,comprising the same emulsion, dye providing substance, and reductivesubstance as used in the light-sensitive material 101 of Example 1.

A light-sensitive material 302 having the same construction as thelight-sensitive material 301 was prepared except that the presentcompound (AF-3) was added to each of 1st layer, 3rd layer, and 5th layerof the light-sensitive material 301 in a molar amount of 0.5 time thatof the respective dye providing substance.

Furthermore, an organic silver salt emulsion was prepared as follows.

20 g of gelatin and 5.9 g of 4-acetylaminophenylpropiolic acid weredissolved in 1,000 ml of a 0.1% aqueous solution of sodium hydroxide and200 ml of ethanol.

The solution was stirred while keeping at a temperature of 40° C.

A solution of 4.5 g of silver nitrate in 200 ml of water was added tothe solution over 5 minutes.

The pH of the dispersion was adjusted to precipitate excess salts whichwere then removed. The pH of the solution was adjusted to 6.3. As aresult, 300 g of a dispersion of an organic silver salt was obtained.

                  TABLE 4                                                         ______________________________________                                        6th Layer:                                                                    Gelatin                 100    mg/m.sup.2                                     Base precursor*.sup.3   500    mg/m.sup.2                                     Film hardener*.sup.6    100    mg/m.sup.2                                     5th Layer: Blue-sensitive emulsion layer                                      Silver bromoiodide emulsion                                                                           400    mg/m.sup.2 as                                  (iodine: 5 mol %)              silver                                         Dimethylsulfamide       180    mg/m.sup.2                                     Organic silver salt emulsion                                                                          100    mg/m.sup.2 as                                                                 silver                                         Base precursor*.sup.3   200    mg/m.sup.2                                     Yellow dye providing substance (1)                                                                    400    mg/m.sup.2                                     Gelatin                 1,300  mg/m.sup.2                                     ED-1                    277    mg/m.sup.2                                     1,5-Diphpenyl-3-pyrazolidone                                                                          60     mg/m.sup.2                                     High boiling solvent*.sup.4                                                                           800    mg/m.sup.2                                     Surface active agent*.sup.2                                                                           100    mg/m.sup.2                                     4th Layer: Interlayer                                                         Gelatin                 1,200  mg/m.sup.2                                     Base precursor*.sup.7   500    mg/m.sup.2                                     3rd Layer: Green-sensitive emulsion Layer                                     Silver bromochloride emulsion                                                                         300    mg/m.sup.2                                     (bromine: 80 mole %)                                                          Dimethylsulfamide       180    mg/m.sup.2                                     Organic silver salt emulsion                                                                          100    mg/m.sup.2 as                                                                 silver                                         ED-1                    277    mg/m.sup.2                                     Base precursor*.sup.3   200    mg/m.sup.2                                     1,5-Diphenyl-3-pyrazolidone                                                                           50     mg/m.sup.2                                     Magenta dye providing substance (2)                                                                   400    mg/m.sup.2                                     Gelatin                 1,200  mg/m.sup.2                                     High boiling solvent*.sup.4                                                                           600    mg/m.sup.2                                     Surface active agent*.sup.2                                                                           100    mg/m.sup.2                                     2nd Layer: Interlayer                                                         Gelatin                 1,000  mg/m.sup.2                                     Base precursor*.sup.7   500    mg/m.sup.2                                     1st Layer: Red-sensitive emulsion layer                                       Silver bromochloride emulsion                                                                         300    mg/m.sup.2 as                                  (bromine: 80 mol %)            silver                                         Benzenesulfonamide      180    mg/m.sup.2                                     Organic silver salt emulsion                                                                          100    mg/m.sup.2 as                                                                 silver                                         Sensitizing dye*.sup.5  8      × 10.sup.-7                                                             mol/m.sup.2                                    Base precursor*.sup.3   200    mg/m.sup.2                                     ED-1                    208    mg/m.sup.2                                     1,5-Diphenyl-3-pyrazolidone                                                                           50     mg/m.sup.2                                     Cyan dye providing substance (8)                                                                      300    mg/m.sup.2                                     Gelatin                 1,200  mg/m.sup.2                                     High boiling solvent*.sup.4                                                                           450    mg/m.sup.2                                     Surface active agent*.sup.2                                                                           100    mg/m.sup.2                                     Support*.sup.1                                                                ______________________________________                                         *.sup.1 Polyethylene terephthalate (film thickness: 100 μm)                ##STR37##                                                                     *.sup.3 Guanidine pchlorophenylsulfonylacetate                                *.sup.4 (isoC.sub.9 H.sub.19 O).sub.3 PO                                      ##STR38##                                                                     *.sup.6 1,2Bis(vinyl sulfonylacetamide)ethane                            

The preparation of a dye fixing material will be described hereinafter.

10 g of poly(methyl acrylate-co-N,N,N-trimethyl-N-vinylbenzylammoniumchloride) (ratio of methyl acrylate to vinylbenzylammonium chloride:1:1) was dissolved in 200 ml of water. The solution was uniformly mixedwith 100 g of 10% lime-treated gelatin. A film hardener was added to themixed solution. The mixed solution was then uniformly coated on a papersupport laminated with polyethylene containing titanium dioxidedispersed therein in an amount such that the wet film thickness reached90 μm. The specimen was dried. The specimen thus dried was used as a dyefixing material comprising a mordant layer.

After being exposed to light as in Example 1, the specimen was uniformlyheated for 20 seconds over a heat block which had been heated to atemperature of 150° C.

The film surface of the dye fixing material was supplied with 20 ml/m²of water. The light-sensitive material thus heated and the dye fixingmaterial were laminated in such a manner that the film surface of thetwo materials faced each other.

The laminate was then heated for 6 seconds over a heat block which hadbeen heated to a temperature of 80° C. The dye fixing material was thenpeeled off the light-sensitive material. As a result, color images wereobtained on the dye fixing material.

The photographic properties are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                               Pre-                                                                   Light- sent                                                                   sensitive                                                                            Com-    Dmax           Dmin                                            Material                                                                             pound           Ma-              Ma-                                   No.    No.     Yellow  genta Cyan Yellow                                                                              genta Cyan                            ______________________________________                                        301    None    1.39    1.58  1.62 0.44  0.58  0.60                                   (con-                                                                         trol)                                                                  302    AF-3    2.00    2.08  2.21 0.24  0.26  0.29                            ______________________________________                                    

The above results show that the light-sensitive material comprising thepresent compounds can provide images having a high density and a lowstain.

EXAMPLE 4

A light-sensitive material 401 was prepared by coating sequentially thebelow mentioned layers on a transparent polyethylene terephthalatesupport.

(I) A dye receiving layer containing:

a) copoly[styrene-N-vinylbenzyl-N,N,N-trihexylammonium chloride] (4.0g/m²) and

b) gelatin (4.0 g/m²).

(II) A white reflecting layer containing:

a) titanium dioxide (22 g/m²) and

b) gelatin (2.2 g/m²).

(III) An opaque layer containing:

a) carbon black (2.7 g/m²) and

b) gelatin (2.7 g/m²).

(IV) A cyan dye providing layer containing:

a) gelatin dispersion of a cyan dye providing compound (15) (0.33mmol/m²) and ED-1 (0.4 mmol/m²) and

b) gelatin (including that in the component a) (1.1 g/m²).

(V) A red-sensitive layer containing:

a) a red-sensitive silver bromoiodide emulsion (0.5 g-Ag/m²) and

b) gelatin (including that in the component a) (1.1 g/m²).

(VI) An interlayer containing:

a) 2,5-di(t-pentadecyl)hydroquinone (0.82 g/m²),

b) vinyl acetate (0.8 g/m²), and

c) gelatin (0.4 g/m²).

(VII) A magenta dye providing layer containing:

a) gelatin dispersion of a magenta dye providing compound (2) (0.3mmol/m²) and ED-1 (0.4 mmol/m²) and

b) gelatin (including that in the component a) (1.1 g/m²).

(VIII) A green sensitive layer containing:

a) green-sensitive silver bromoiodide emulsion (0.5 g-Ag/m²) and

b) gelatin (including that in the component a) (1.1 g/m²).

(IX) Same as the interlayer (VI)

(X) A yellow dye providing layer containing:

a) gelatin dispersion of a yellow dye providing compound (10) (0.5mmol/m²) and ED-1 (0.6 mmol/m²) and

b) gelatin (including that in the component a) (1.1 g/m²).

(XI) A blue-sensitive layer containing:

a) blue-sensitive silver bromoiodide emulsion (0.5 g/m²) and

b) gelatin (including that in the component a) (1.1 g/m²).

(XII) A protective layer containing:

a) latex of polyethylene acrylate (0.9 g/m²),

b) Tinuvin® (0.5 g/m²),

c) triacryloyl perhydrotriazine as film hardener (0.026 g/m²), and

d) gelatin (1.3 g/m²).

A light-sensitive material 402 having the same composition as thelight-sensitive material 401 was prepared in the same manner as in thelight-sensitive material 401 except that the compound AF-9 of thepresent invention was added to the (IV) layer, (VII) layer, and (X)layer of the light-sensitive material 401 in a molar amount of 0.4 timethat of the respective dye providing substance.

A cover sheet was prepared by sequentially coating the undermentionedlayers on a transparent polyethyleneterephthalate film.

(I) An acid neutralization layer containing:

a) polyacrylic acid (17 g/m²),

b) N-hydroxysuccinimidobenzene sulfonate (0.06 g/m²), and

c) ethylene glycol (0.5 g/m²).

(II) A timing layer comprising a 2-μm thick coat of cellulose acetate(degree of acetylation: 54%).

(III) A timing layer comprising a 4-μm thick coat of a latex ofcopolymer of vinylidene chloride and acrylic acid.

A processing solution having the undermentioned composition wasprepared.

    ______________________________________                                        Potassium hydroxide       48     g                                            4-Hydroxymethyl-4-methyl-1-p-tolyl-3-                                                                   10     g                                            pyrazolidinone                                                                5-Methylbenzenetriazole   1.5    g                                            Sodium sulfite            1.5    g                                            Potassium bromide         1      g                                            Benzyl alcohol            1.5    ml                                           Carboxymethyl cellulose   6.1    g                                            Carbon black              150    g                                            Water to make             1      l                                            ______________________________________                                    

The light-sensitive materials 401 and 402 were exposed to light througha wedge. The cover sheet was then superimposed on these light-sensitivematerials thus exposed. The above described processing solution wasuniformly spread over between the two sheets to a thickness of 80 μm bymeans of a pair of superposed rollers.

One hour after processing, sensitometry was conducted. The results areshown in Table 6.

                  TABLE 6                                                         ______________________________________                                               Pre-                                                                   Light- sent                                                                   sensitive                                                                            Com-    Dmax           Dmin                                            Material                                                                             pound           Ma-              Ma-                                   No.    No.     Yellow  genta Cyan Yellow                                                                              genta Cyan                            ______________________________________                                        401    None    1.58    1.70  1.98 0.24  0.25  0.38                                   (con-                                                                         trol)                                                                  402    AF-9    1.96    2.01  2.22 0.22  0.24  0.29                            ______________________________________                                    

Thus, a color image having less stain in the white background and ahigher transfer density was obtained.

EXAMPLE 5

The preparation of a gelatin dispersion of a dye providing substancewill be described hereinafter.

20 ml of cyclohexanone was added to 5.5 g of a dye providing substance(30), 6 g of a reductive substance of the structural formula: ##STR39##0.5 g of succinic acid-2-ethyl-sodium hexylestersulfonate, and 5 g oftri-cresyl phosphate (TCP). The admixture was heated to a temperature ofabout 60° C. to further dissolution. The solution and 100 g of a 10%gelatin solution were mixed with stirring. The mixture was thensubjected to homogenization by means of a homogenizer at 10,000 rpm for10 minutes.

The preparation of light-sensitive coating solution will be describedhereinafter.

    ______________________________________                                        (a)    Silver bromochloride emulsion                                                                          10    g                                              (emulsion for 1st layer in Example 1)                                  (b)    Dispersion of a dye providing substance                                                                3.5 g                                         (c)    5% aqueous solution of compound of                                                                     1.5   ml                                             the formula:                                                                   ##STR40##                                                             (d)    Basic zinc carbonate     3.0   g                                              (20% aqueous dispersion)                                               (e)    4-Hydroxymethyl-4-methyl-1-                                                                            1     ml                                             phenyl-3-pyrazolidone                                                         (3% methanol solution)                                                 ______________________________________                                    

The above described components (a) to (e) were mixed and heated tofurther dissolution. The coating solution thus prepared was then coatedon a polyethylene terephthate film to a wet film thickness of 30 μm anddried.

A protective layer having the undermentioned composition was coated onthe film thus coated to a wet film thickness of 30 μm and dried toprepare a light-sensitive material 501.

    ______________________________________                                        (a)    Gelatin (10% aqueous solution)                                                                       30    g                                         (b)    2% Aqueous solution of 1,2-bis-                                                                      5     ml                                               (vinyl sulfonylacetamide)ethane                                        (c)    Water                  70    ml                                        ______________________________________                                    

A light-sensitive material 502 was prepared in the same manner as in thelight-sensitive material 501 except that the present compound AF-9 wasadded to a gelatin dispersion of a dye providing substance of thelight-sensitive material 501 in a molar amount of 0.4 time that of thedye providing substance.

These light-sensitive materials were then image-wise exposed to a lightof 2,000 lux from a tungsten lamp for 1 second.

As a dye fixing material there was used the same dye fixing material asin Example 1.

The light sensitive materials 501 and 502 were wetted by immersing inwater. These light-sensitive materials were squeezed to remove surfacewater. These light-sensitive materials were then laminated with the dyefixing material in such a manner that the film surface of the two sheetsfaced each other.

The laminate was then heated for 20 seconds by means of a press whichhad been temperature-adjusted so as to keep the temperature of the filmat 80° C. The light-sensitive material was then peeled off the dyefixing element.

The image density of images on the dye fixing material was measured. Theresults are shown below.

    ______________________________________                                        Light-sensitive                                                               Material No. Maximum Density                                                                            Minimum Density                                     ______________________________________                                        501 (control)                                                                              1.65         0.24                                                502          2.03         0.22                                                ______________________________________                                    

With the present compound, an image having a high maximum density and alow stain was obtained.

EXAMPLE 6

Light-sensitive materials 601 to 605 having the same construction as thelight-sensitive material 101 were prepared in the same manner as in thelight-sensitive material 101 except that the present compounds AF-76,AF-91, AF-96, AF-97, and AF-98 were separately added to each of 1stlayer, 3rd layer, and 5th layer of the light-sensitive material 101 inExample 1 in a molar amount of 0.5 time that of the respective dyeproviding substance.

These light-sensitive materials were processed with the same dye fixingmaterial as used in Example 1 in the same manner as in Example 1. As aresult, the light-sensitive materials 601 to 605 provided a higherD_(max) and a lower D_(min) than the light-sensitive material 101.

EXAMPLE 7

Light-sensitive materials 701 and 702 having the same construction asthe light-sensitive material 201 except that the present compound AF-10or AF-98 was added to each of 2nd layer and 4th layer of thelight-sensitive material 201 in Example 2 in an amount of 0.2 mmol/m².

These light-sensitive materials were processed in the same manner as inExample 2. Photographic properties shown in Table 7 were obtained.

                  TABLE 7                                                         ______________________________________                                               Pre-                                                                   Light- sent                                                                   sensitive                                                                            Com-    Dmax           Dmin                                            Material                                                                             pound           Ma-              Ma-                                   No.    No.     Yellow  genta Cyan Yellow                                                                              genta Cyan                            ______________________________________                                        201    None    1.52    1.63  1.75 0.25  0.29  0.29                                   (con-                                                                         trol)                                                                  701    AF-10   1.95    2.03  2.10 0.22  0.24  0.26                            702    AF-98   1.90    2.00  2.02 0.23  0.24  0.27                            ______________________________________                                    

Thus, it was found that the present compounds can exert the effect evenwhen added to an interlayer.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A color light-sensitive material, comprising on asupport at least a light-sensitive silver halide, a binder, a dyeproviding substance which provides a mobile dye in inverse relationshipto the reduction reaction of silver ion to silver, and a developmentinhibitor precursor of the general formula (II): ##STR41## wherein AFrepresents a group which serves as a development inhibitor after beingreleased; wherein EAG represents an electron accepting group; Nrepresents a nitrogen atom; X represents an oxygen atom (--O--), sulfuratom (--S--), or a nitrogen atom-containing group, ##STR42## R¹, R² andR³ each represents a simple bond or a group other than a hydrogen atom,with the proviso that any two of R¹, R², R³, and EAG may be bonded toeach other to form a ring; Time represents a group which releases AFthrough a reaction triggered by the cleavage of the N--X bond; trepresents an integer of 0 or 1; the solid lines indicate a bond; andthe broken lines indicate that at least one thereof represents a bond;wherein the dye providing substance is a positive dye providingsubstance represented by general formula (CII); wherein the N--X bond isreduced by a reductive substance to undergo cleavage which causes therelease of a mobile dye; ##STR43## wherein Dye represents a groupproviding a compound which serves as a mobile dye after being reduced;and R¹, R², EAG, Time, t, N, X, broken lines, and solid lines have thesame meanings as defined in the general formula (II), and wherein theamount of the compound of general formula (II) is from 1×10⁻³ to 1×10²mols per mol of the positive dye providing substance.
 2. A colorlight-sensitive material as in claim 1, wherein said compound of thegeneral formula (II) is represented by the general formula (III):##STR44## wherein Y represents a divalent connecting group; R⁴represents an atomic group which is bonded to X and Y to form a five- toeight-membered heterocyclic ring together with nitrogen atom; and N, X,EAG, Time, t, and AF are as defined in claim
 1. 3. A colorlight-sensitive material as in claim 1, wherein X is an oxygen atom. 4.A color light-sensitive material as in claim 1, wherein R¹ and R³ areeach substituted or unsubstituted alkyl group, a substituted orunsubstituted aryl group, a substituted or unsubstituted heterocyclicresidual group, a substituted or unsubstituted acyl group, or asubstituted or unsubstituted sulfonyl group; R² is a substituted orunsubstituted acyl group or a substituted or unsubstituted sulfonylgroup; and any two of R¹, R² and R³ may be bonded to each other to forma 5-membered to 8-membered ring.
 5. A color light-sensitive material asin claim 1, wherein AF represents a mercapto group bonded to aheterocyclic ring selected from the group consisting of a substituted orunsubstituted mercapto azole, a substituted or unsubstituted mercaptoazaindene, and a substituted or unsubstituted mercapto pyrimidine.
 6. Acolor light-sensitive material as in claim 1, wherein AF comprises aheterocyclic compound capable of producing imino silver selected fromthe group consisting of substituted or unsubstituted benzotriazoles,substituted or unsubstituted indazoles, and substituted or unsubstitutedbenzimidazoles.
 7. A color light-sensitive material as in claim 1,wherein AF represents a development inhibitor which is released from anoxidation-reduction nucleus in the general formula (I) by a reactionfollowing an oxidation-reduction reaction in the development step.
 8. Acolor light-sensitive material as in claim 7, wherein AF is selectedfrom the group consisting of1-(3-phenoxycarbonylphenyl)-5-mercaptotetrazole,1-(4-phenoxycarbonylphenyl)-5-mercaptotetrazole,1-(3-maleimidophenyl)-5-mercaptotetrazole,5-(phenoxycarbonyl)benzotriazole,5-(p-cyanophenoxycarbonyl)benzotriazole,2-phenoxycarbonylmethylthio-5-mercapto-1,3,4-thiadiazole,5-nitro-3-phenoxycarbonylindazole,5-phenoxycarbonyl-2-mercaptobenzimidazole,5-(2,3-dichloropropyloxycarbonyl)benzotriazole,5-benzyloxycarbonylbenzotriazole,5-(butylcarbamoylmethoxycarbonyl)benzotriazole,5-(butoxycarbonylmethoxycarbonyl)benzotriazole,1-(4-benzoyloxyphenyl)-5-mercaptotetrazole,5-(2-methanesulfonylethoxycarbonyl)-2-mercaptobenzothiazole,1-[4-(2-chloroethoxycarbonyl)phenyl]-2-mercaptoimidazole,2-[3-(thiophene-2-ylcarbonyl)propyl]thio-5-mercapto-1,3,4-thiadiazole,5-cinnamoylaminobenzotriazole,1-(3-vinylcarbonylphenyl)-5-mercaptotetrazole,5-succinimidomethylbenzotriazole,2-[4-succinimidophenyl]-5-mercapto-1,3,4-oxadiazole,3-[4-(benzo-1,2-isothiazole-3-oxo-1,1-dioxy-2-yl)phenyl]-5-mercapto-4-methyl-1,2,4-triazole,and 6-phenoxycarbonyl-2-mercaptobenzoxazole.
 9. A color light-sensitivematerial as in claim 1, wherein the development inhibitor precursor ofthe general formula (I) is present in an amount of from 1×10⁻⁷ to 1 molper mol of silver halide or 1×10⁻³ to 1×10⁻² mol per mol of positive dyeproviding substance.
 10. The color light-sensitive material as in claim1, wherein the amount of the compound of general formula (II) is from1×10⁻² to 10 mols per mol of the positive dye providing substance.